Probing the effects of polymers on the early stages of calcium carbonate formation by stoichiometric co-titration.

Potentiometric titrations are a powerful tool to study the early stages of the precipitation of minerals such as calcium carbonate and were used among others for the discovery and characterisation of key precursors like prenucleation clusters. Here we present a modified procedure for conducting such titration experiments, in which the reactants (i.e. calcium and (bi)carbonate ions) are added simultaneously in stoichiometric amounts, while both the amount of free calcium and the optical transmission of the solution are monitored online. Complementarily, the species occurring at distinct stages of the crystallisation process were studied using cryogenic transmission electron microscopy. This novel routine was applied to investigate CaCO3 nucleation in the absence and presence of polymeric additives with different chemical functionalities. The obtained results provide new insights into the critical steps underlying nucleation and subsequent ripening, such as the role of liquid mineral-rich phases and their transformation into solid particles. The studied polymers proved to interfere at multiple stages along the complex mineralisation pathway of calcium carbonate, with both the degree and mode of interaction depending on the chosen polymer chemistry. In this way, the methodology developed in this work allows the mechanisms of antiscalants - or crystallisation modifiers in general - to be elucidated at an advanced level of detail.

Small-Molecular-Weight Additives Modulate Calcification by Interacting with Prenucleation Clusters on the Molecular Level.

Small-molecular-weight (MW) additives can strongly impact amorphous calcium carbonate (ACC), playing an elusive role in biogenic, geologic, and industrial calcification. Here, we present molecular mechanisms by which these additives regulate stability and composition of both CaCO3 solutions and solid ACC. Potent antiscalants inhibit ACC precipitation by interacting with prenucleation clusters (PNCs); they specifically trigger and integrate into PNCs or feed PNC growth actively. Only PNC-interacting additives are traceable in ACC, considerably stabilizing it against crystallization. The selective incorporation of potent additives in PNCs is a reliable chemical label that provides conclusive chemical evidence that ACC is a molecular PNC-derived precipitate. Our results reveal additive-cluster interactions beyond established mechanistic conceptions. They reassess the role of small-MW molecules in crystallization and biomineralization while breaking grounds for new sustainable antiscalants.

The nano- and meso-scale structure of amorphous calcium carbonate.

Understanding the underlying processes of biomineralization is crucial to a range of disciplines allowing us to quantify the effects of climate change on marine organisms, decipher the details of paleoclimate records and advance the development of biomimetic materials. Many biological minerals form via intermediate amorphous phases, which are hard to characterize due to their transient nature and a lack of long-range order. Here, using Monte Carlo simulations constrained by X-ray and neutron scattering data together with model building, we demonstrate a method for determining the structure of these intermediates with a study of amorphous calcium carbonate (ACC) which is a precursor in the bio-formation of crystalline calcium carbonates. We find that ACC consists of highly ordered anhydrous nano-domains of approx. 2 nm that can be described as nanocrystalline. These nano-domains are held together by an interstitial net-like matrix of water molecules which generate, on the mesoscale, a heterogeneous and gel-like structure of ACC. We probed the structural stability and dynamics of our model on the nanosecond timescale by molecular dynamics simulations. These simulations revealed a gel-like and glassy nature of ACC due to the water molecules and carbonate ions in the interstitial matrix featuring pronounced orientational and translational flexibility. This allows for viscous mobility with diffusion constants four to five orders of magnitude lower than those observed in solutions. Small and ultra-small angle neutron scattering indicates a hierarchically-ordered organization of ACC across length scales that allow us, based on our nano-domain model, to build a comprehensive picture of ACC formation by cluster assembly from solution. This contribution provides a new atomic-scale understanding of ACC and provides a framework for the general exploration of biomineralization and biomimetic processes.

Bioinspired Materials: From Living Systems to New Concepts in Materials Chemistry.

Nature successfully employs inorganic solid-state materials (i.e., biominerals) and hierarchical composites as sensing elements, weapons, tools, and shelters. Optimized over hundreds of millions of years under evolutionary pressure, these materials are exceptionally well adapted to the specifications of the functions that they perform. As such, they serve today as an extensive library of engineering solutions. Key to their design is the interplay between components across length scales. This hierarchical design-a hallmark of biogenic materials-creates emergent functionality not present in the individual constituents and, moreover, confers a distinctly increased functional density, i.e., less material is needed to provide the same performance. The latter aspect is of special importance today, as climate change drives the need for the sustainable and energy-efficient production of materials. Made from mundane materials, these bioceramics act as blueprints for new concepts in the synthesis and morphosynthesis of multifunctional hierarchical materials under mild conditions. In this review, which also may serve as an introductory guide for those entering this field, we demonstrate how the pursuit of studying biomineralization transforms and enlarges our view on solid-state material design and synthesis, and how bioinspiration may allow us to overcome both conceptual and technical boundaries.