Stabilization and crystallization mechanism of amorphous calcium carbonate.

Amorphous phases hold great promise in diverse applications and are widely used by organisms as precursors to produce biominerals with complex morphologies and excellent properties. However, the stabilization and crystallization mechanisms of amorphous phases are not fully understood, especially in the presence of additives. Here, using amorphous calcium carbonate (ACC) as the model system, we systematically investigate the crystallization pathways of amorphous phases in the presence of poly(Aspartic acid) (pAsp) with various chain lengths.

Strong and Tough MXene Bridging-induced Conductive Nacre.

Nacre is a classic model, providing an inspiration for fabricating high-performance bulk nanocomposites with the two-dimensional platelets. However, the "brick" of nacre, aragonite platelet, is an ideal building block for making high-performance bulk nanocomposites. Herein, we demonstrated a strong and tough conductive nacre through reassembling aragonite platelets with bridged by MXene nanosheets and hydrogen bonding, not only providing high mechanical properties but also excellent electrical conductivity.

Myriad Mapping of nanoscale minerals reveals calcium carbonate hemihydrate in forming nacre and coral biominerals.

Calcium carbonate (CaCO) is abundant on Earth, is a major component of marine biominerals and thus of sedimentary and metamorphic rocks and it plays a major role in the global carbon cycle by storing atmospheric CO into solid biominerals. Six crystalline polymorphs of CaCO are known-3 anhydrous: calcite, aragonite, vaterite, and 3 hydrated: ikaite (CaCO·6HO), monohydrocalcite (CaCO·1HO, MHC), and calcium carbonate hemihydrate (CaCO·½HO, CCHH). CCHH was recently discovered and characterized, but exclusively as a synthetic material, not as a naturally occurring mineral.

Bioprocess inspired formation of calcite mesocrystals by cation-mediated particle attachment mechanism.

Calcite mesocrystals were proposed, and have been widely reported, to form in the presence of polymer additives via oriented assembly of nanoparticles. However, the formation mechanism and the role of polymer additives remain elusive. Here, inspired by the biomineralization process of sea urchin spine comprising magnesium calcite mesocrystals, we show that calcite mesocrystals could also be obtained via attachment of amorphous calcium carbonate (ACC) nanoparticles in the presence of inorganic zinc ions.

Bioinspired Strategy for Efficient TiO/Au/CdS Photocatalysts Based On Mesocrystal Superstructures in Biominerals and Charge-Transfer Pathway in Natural Photosynthesis.

Natural photosynthesis involves an efficient charge-transfer pathway through exquisitely arranged photosystems and electron transport intermediates, which separate photogenerated carriers to realize high quantum efficiency. It inspires a rational design construction of artificial photosynthesis systems and the architectures of semiconductors are essential to achieve optimal performance. Of note, biomineralization processes could form various mesocrystals with well-ordered superstructures for unique optical applications.

Mineralization of calcium phosphate induced by a silk fibroin film under different biological conditions.

Silk fibroin is a promising biomaterial that has been used for tissue engineering applications. However, the influence of silk fibroin on the mineralization of calcium phosphate in different biological environments has not been discussed before. In this work, we fabricated organized silk fibroin film as the organic framework and amorphous calcium phosphate (ACP) deposited on the films as precursors.

Nanocage Ferritin Reinforced Polyacrylamide Hydrogel for Wearable Flexible Strain Sensors.

Biocomposite hydrogels are promising for applications in wearable flexible strain sensors. Nevertheless, the existing biocomposite hydrogels are still hard to meet all requirements, which limits the practical application. Here, inspired by the structure and composition of natural ferritin, we design a PAAm-Ferritin hybrid hydrogel through a facile method.

Room-temperature growth of fluorapatite/CaCO heterogeneous structured composites inspired by human tooth.

Organisms can synthesize heterogeneous structures with excellent mechanical properties through mineralization, the most typical of which are teeth. The tooth is an extraordinarily resilient bi-layered material that is composed of external enamel perpendicular to the tooth surface and internal dentin parallel to the tooth surface. The synthesis of enamel-like heterostructures with good mechanical properties remains an elusive challenge.

Pressure-induced crystallization and densification of amorphized calcium carbonate hexahydrate controlled by interfacial water.

Amorphous calcium carbonate (ACC) is widely known as a metastable precursor in the formation of crystalline calcium carbonate biominerals. However, the exact role of water during the crystallization of ACC remains elusive. Here, a novel ACC with high specific surface area and nanopores is synthesized by solvent-induced dehydration and amorphization of crystalline calcium carbonate hexahydrate (ikaite), denoted as I-ACC.

Silk fibroin directs the formation of monetite nanocrystals and their assembly into hierarchical composites.

Natural biominerals are usually composite materials produced through mineralization of inorganic crystals within an organic matrix. Silk fibroin is known to be capable of directing the nucleation and growth of hydroxyapatite crystals. Here, we used silk films as the substrate to induce the mineralization of calcium phosphate.

Bioprocess-inspired synthesis of multilayered chitosan/CaCO composites with nacre-like structures and high mechanical properties.

The formation of natural structures found in biological systems is wonderful and can be completed at ambient temperatures in contrast to artificial technologies wherein harsh conditions are common prerequisites. A new research direction, "bioprocess inspired manufacturing", is proposed for fabricating advanced materials with novel structures and functions. Nacre consists of an ordered multilayer structure of crystalline calcium carbonate lamellae separated by organic layers exhibiting mechanical toughness, which transcends that of its constituent components.

Hydroxyapatite-reinforced alginate fibers with bioinspired dually aligned architectures.

Biological materials have excellent mechanical properties due to their organized structures from nano- to macro-scale. Artificial manufacture of materials with anisotropic microstructures still remains challenging. We described a stress-induced method to fabricate anisotropic alginate fibers.

Bioprocess-Inspired Room-Temperature Synthesis of Enamel-like Fluorapatite/Polymer Nanocomposites Controlled by Magnesium Ions.

Tooth enamel is composed of arrayed fluorapatite (FAP) or hydroxyapatite nanorods modified with Mg-rich amorphous layers. Although it is known that Mg plays an important role in the formation of enamel, there is limited research on the regulatory role of Mg in the synthesis of enamel-like materials. Therefore, we focus on the regulatory behavior of Mg in the fabrication of biomimetic mineralized enamel-like structural materials.

Bioinspired 3D Printable, Self-Healable, and Stretchable Hydrogels with Multiple Conductivities for Skin-like Wearable Strain Sensors.

Bioinspired hydrogels have promising prospects in applications such as wearable devices, human health monitoring equipment, and soft robots due to their multifunctional sensing properties resembling natural skin. However, the preparation of intelligent hydrogels that provide feedback on multiple electronic signals simultaneously, such as human skin receptors, when stimulated by external contact pressure remains a substantial challenge. In this study, we designed a bioinspired hydrogel with multiple conductive capabilities by incorporating carbon nanotubes into a chelate of calcium ions with polyacrylic acid and sodium alginate.

Particle-attachment crystallization facilitates the occlusion of micrometer-sized in calcium carbonate crystals with stable fluorescence.

Inspired from the occlusion of macromolecules in mineral crystals during the biomineralization process, the occlusion mechanism of functional guest species into a host matrix is gradually revealed in artificial systems. However, the guest species within calcite crystals are limited to the nanometer scale. Herein, using amorphous calcium carbonate (ACC) as a precursor and taking advantage of the crystallization of vaterite by the attachment of ACC nanoparticles, micrometer-sized modified Escherichia coli (E.

Three-dimensional structural interrelations between cells, extracellular matrix, and mineral in normally mineralizing avian leg tendon.

The spatial-temporal relationship between cells, extracellular matrices, and mineral deposits is fundamental for an improved understanding of mineralization mechanisms in vertebrate tissues. By utilizing focused ion beam-scanning electron microscopy with serial surface imaging, normally mineralizing avian tendons have been studied with nanometer resolution in three dimensions with volumes exceeding tens of micrometers in range. These parameters are necessary to yield sufficiently fine ultrastructural details while providing a comprehensive overview of the interrelationships between the tissue structural constituents.

Synthesis of monodisperse rod-shaped silica particles through biotemplating of surface-functionalized bacteria.

Mesoporous silica particles of controlled size and shape are potentially beneficial for many applications, but their usage may be limited by the complex procedure of fabrication. Biotemplating provides a facile approach to synthesize materials with desired shapes. Herein, a bioinspired design principle is adopted through displaying silaffin-derived 5R5 proteins on the surface of Escherichia coli by genetic manipulations.

Unveiling the Origin of the High Catalytic Activity of Ultrathin 1T/2H MoSe Nanosheets for the Hydrogen Evolution Reaction: A Combined Experimental and Theoretical Study.

2 D transition metal dichalcogenide materials with layered nanostructures and specific phases usually exhibit excellent catalytic activities for the hydrogen evolution reaction (HER). A facile solvothermal process was used to prepare ultrathin noble-metal-free 2 D biphasic MoSe nanosheets composed of a metastable metallic 1T phase and a semiconducting 2H phase. High metallic 1T phase content and few-layer-thick MoSe nanosheets were obtained by tuning the amount of NaBH used in the reaction.

Growth and regrowth of adult sea urchin spines involve hydrated and anhydrous amorphous calcium carbonate precursors.

In various mineralizing marine organisms, calcite or aragonite crystals form through the initial deposition of amorphous calcium carbonate (ACC) phases with different hydration levels. Using X-ray PhotoEmission Electron spectroMicroscopy (X-PEEM), ACCs with varied spectroscopic signatures were previously identified. In particular, ACC type I and II were recognized in embryonic sea urchin spicules.

A hydrated crystalline calcium carbonate phase: Calcium carbonate hemihydrate.

As one of the most abundant materials in the world, calcium carbonate, CaCO, is the main constituent of the skeletons and shells of various marine organisms. It is used in the cement industry and plays a crucial role in the global carbon cycle and formation of sedimentary rocks. For more than a century, only three polymorphs of pure CaCO-calcite, aragonite, and vaterite-were known to exist at ambient conditions, as well as two hydrated crystal phases, monohydrocalcite (CaCO·1HO) and ikaite (CaCO·6HO).

The Crystallization of Amorphous Calcium Carbonate is Kinetically Governed by Ion Impurities and Water.

Many organisms use amorphous calcium carbonate (ACC) and control its stability by various additives and water; however, the underlying mechanisms are yet unclear. Here, the effect of water and inorganic additives commonly found in biology on the dynamics of the structure of ACC during crystallization and on the energetics of this process is studied. Total X-ray scattering and pair distribution function analysis show that the short- and medium-range order of all studied ACC samples are similar; however, the use of in situ methodologies allow the observation of small structural modifications that are otherwise easily overlooked.

Additives influence the phase behavior of calcium carbonate solution by a cooperative ion-association process.

Amorphous calcium carbonate (ACC) has been widely found in biomineralization, both as a transient precursor and a stable phase, but how organisms accurately control its formation and crystallization pathway remains unclear. Here, we aim to illuminate the role of biologically relevant additives on the phase behaviour of calcium carbonate solution by investigating their effects on the formation of ACC. Results show that divalent cations like magnesium (Mg) ions and negatively charged small organic molecules like aspartic acid (Asp) have little/no effect on ACC formation.