Fiona C. Meldrum

Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems

2.3. Amorphous Minerals 4354 3. Biological Routes to Controlling Morphology 4354 3.1. General Mechanisms 4356 3.1.1. Soluble and Insoluble Organic Molecules 4356 3.1.2. Control over Crystal Polymorph 4357 3.1.3. Control over Crystal Orientation 4359 3.2. Single-Crystal Biominerals 4359 3.2.1. Organic and Inorganic Soluble Additives 4360 3.2.2. Templating of Single-Crystal Morphologies 4361 3.3. Polycrystalline Biominerals 4366 3.3.1. Nacre Formation in Mollusks 4366 3.3.2. ForaminiferasA Biogenic Mesocrystal 4368 3.4. Amorphous Biominerals 4370 3.4.1. Silicification in Diatoms 4370 3.4.2. In Vitro Studies of Silicification in Diatoms 4371 4. Bioinspired Routes to Controlling Crystal Morphologies 4371

Crystallization at Inorganic-organic Interfaces: Biominerals and Biomimetic Synthesis

Crystallization is an important process in a wide range of scientific disciplines including chemistry, physics, biology, geology, and materials science. Recent investigations of biomineralization indicate that specific molecular interactions at inorganic-organic interfaces can result in the controlled nucleation and growth of inorganic crystals. Synthetic systems have highlighted the importance of electrostatic binding or association, geometric matching (epitaxis), and stereochemical correspondence in these recognition processes. Similarly, organic molecules in solution can influence the morphology of inorganic crystals if there is molecular complementarity at the crystal-additive interface. A biomimetic approach based on these principles could lead to the development of new strategies in the controlled synthesis of inorganic nanophases, the crystal engineering of bulk solids, and the assembly of organized composite and ceramic materials.

Crystallization by particle attachment in synthetic, biogenic, and geologic environments

Growing crystals by attaching particles Crystals grow in a number a ways, including pathways involving the assembly of other particles and multi-ion complexes. De Yoreo et al. review the mounting evidence for these nonclassical pathways from new observational and computational techniques, and the thermodynamic basis for these growth mechanisms. Developing predictive models for these crystal growth and nucleation pathways will improve materials synthesis strategies. These approaches will also improve fundamental understanding of natural processes such as biomineralization and trace element cycling in aquatic ecosystems. Science, this issue 10.1126/science.aaa6760 Materials nucleate and grow by the assembly of small particles and multi-ion complexes. BACKGROUND Numerous lines of evidence challenge the traditional interpretations of how crystals nucleate and grow in synthetic and natural systems. In contrast to the monomer-by-monomer addition described in classical models, crystallization by addition of particles, ranging from multi-ion complexes to fully formed nanocrystals, is now recognized as a common phenomenon. This diverse set of pathways results from the complexity of both the free-energy landscapes and the reaction dynamics that govern particle formation and interaction. Whereas experimental observations clearly demonstrate crystallization by particle attachment (CPA), many fundamental aspects remain unknown—particularly the interplay of solution structure, interfacial forces, and particle motion. Thus, a predictive description that connects molecular details to ensemble behavior is lacking. As that description develops, long-standing interpretations of crystal formation patterns in synthetic systems and natural environments must be revisited. Here, we describe the current understanding of CPA, examine some of the nonclassical thermodynamic and dynamic mechanisms known to give rise to experimentally observed pathways, and highlight the challenges to our understanding of these mechanisms. We also explore the factors determining when particle-attachment pathways dominate growth and discuss their implications for interpreting natural crystallization and controlling nanomaterials synthesis. ADVANCES CPA has been observed or inferred in a wide range of synthetic systems—including oxide, metallic, and semiconductor nanoparticles; and zeolites, organic systems, macromolecules, and common biomineral phases formed biomimetically. CPA in natural environments also occurs in geologic and biological minerals. The species identified as being responsible for growth vary widely and include multi-ion complexes, oligomeric clusters, crystalline or amorphous nanoparticles, and monomer-rich liquid droplets. Particle-based pathways exceed the scope of classical theories, which assume that a new phase appears via monomer-by-monomer addition to an isolated cluster. Theoretical studies have attempted to identify the forces that drive CPA, as well as the thermodynamic basis for appearance of the constituent particles. However, neither a qualitative consensus nor a comprehensive theory has emerged. Nonetheless, concepts from phase transition theory and colloidal physics provide many of the basic features needed for a qualitative framework. There is a free-energy landscape across which assembly takes place and that determines the thermodynamic preference for particle structure, shape, and size distribution. Dynamic processes, including particle diffusion and relaxation, determine whether the growth process follows this preference or another, kinetically controlled pathway. OUTLOOK Although observations of CPA in synthetic systems are reported for diverse mineral compositions, efforts to establish the scope of CPA in natural environments have only recently begun. Particle-based mineral formation may have particular importance for biogeochemical cycling of nutrients and metals in aquatic systems, as well as for environmental remediation. CPA is poised to provide a better understanding of biomineral formation with a physical basis for the origins of some compositions, isotopic signatures, and morphologies. It may also explain enigmatic textures and patterns found in carbonate mineral deposits that record Earth’s transition from an inorganic to a biological world. A predictive understanding of CPA, which is believed to dominate solution-based growth of important semiconductor, oxide, and metallic nanomaterials, promises advances in nanomaterials design and synthesis for diverse applications. With a mechanism-based understanding, CPA processes can be exploited to produce hierarchical structures that retain the size-dependent attributes of their nanoscale building blocks and create materials with enhanced or novel physical and chemical properties. Major gaps in our understanding of CPA. Particle attachment is influenced by the structure of solvent and ions at solid-solution interfaces and in confined regions of solution between solid surfaces. The details of solution and solid structure create the forces that drive particle motion. However, as the particles move, the local structure and corresponding forces change, taking the particles from a regime of long-range to short-range interactions and eventually leading to particle-attachment events. Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. The particles involved in these nonclassical pathways to crystallization are diverse, in contrast to classical models that consider only the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle-attachment processes and show that multiple pathways result from the interplay of free-energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects, particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemble behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems, biominerals, and patterns of mineralization in natural environments.

Morphological influence of magnesium and organic additives on the precipitation of calcite

Calcium carbonate was precipitated from saturated solutions of calcium bicarbonate in the presence of magnesium and organic additives in order to investigate the effect of Mg-incorporation on calcite morphologies. A range of concentrations of Mg and organic additives were investigated, and the structure, composition and morphologies of the crystals were determined using X-ray diffraction and electron microscopy. The action of the organic additives in Mg-free solutions was highly specific, producing elongated single calcite crystals. A much wider range of calcite morphologies was observed in the presence of both Mg and organic additives, and a transition from single crystal to aggregates occurred on increasing the Mg concentration. The MgCO3 content of the crystals increased with the solution Mg concentration, but showed little correlation with the organic additive concentration. Single crystals of magnesian calcite containing up to approximately 10% MgCO3 were prepared, and typically exhibited rounded faces and edges. The polycrystalline aggregates had morphologies ranging from dumbbells to spheres and occluded up to about 22% MgCO3. The experiments suggest that Mg2+ ions act in combination with organic additives to affect calcite morphologies by mechanisms such as adsorption on specific crystal faces which inhibits growth, and by altering the calcite nucleation and growth processes.

Structure-property relationships of a biological mesocrystal in the adult sea urchin spine

Structuring over many length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, show how Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature’s demonstration of how crystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials.

Electron Microscopy Study of Magnetosomes in a Cultured Coccoid Magnetotactic Bacterium

Intracellular magnetite (Fe3O4) crystals produced by the magnetotactic bacterium MC-1 were analysed by transmission electron microscopy (TEM). Strain MC-1 represents the first-reported isolation of a coccoid magnetotactic bacterium in axenic culture. The magnetosomes of this bacterium displayed a pseudo-hexagonal prismatic habit, were elongated along <111> the crystallographic direction, and were truncated by {111}, {100} and {110} faces. The presence of {111} truncations represents a modification of the magnetosome morphology previously determined for those in other coccoid bacteria. Study of immature crystals produced by strain MC-1 showed that the crystal morphology was controlled even at early stages of development. Changes in the culture media affected both the number and shape of the bacterial magnetite crystals. Cells grown in an acetate-containing medium contained on average more crystals than those in cells grown in a sulphide-containing medium. Crystals synthesized in the acetate-grown cells tended to be less truncated than those in the sulphide-grown cells. No iron sulphide minerals, such as greigite, were observed in cells grown in the presence of sulphide.

Synthesis of Single Crystals of Calcite with Complex Morphologies

Calcium carbonate single crystal structures (see Figure) have been precipitated in polymer membranes with bicontinuous structures whereby the morphologies are dictated by the polymer membrane. The single crystals exhibit intricate, sponge-like morphologies, demonstrating that synthesis of single crystals with complex structure is not restricted to the realm of biomineralization.

Dehydration and crystallization of amorphous calcium carbonate in solution and in air

The mechanisms by which amorphous intermediates transform into crystalline materials are poorly understood. Currently, attracting enormous interest is the crystallization of amorphous calcium carbonate, a key intermediary in synthetic, biological and environmental systems. Here we attempt to unify many contrasting and apparently contradictory studies by investigating this process in detail. We show that amorphous calcium carbonate can dehydrate before crystallizing, both in solution and in air, while thermal analyses and solid-state nuclear magnetic resonance measurements reveal that its water is present in distinct environments. Loss of the final water fraction—comprising less than 15% of the total—then triggers crystallization. The high activation energy of this step suggests that it occurs by partial dissolution/recrystallization, mediated by surface water, and the majority of the particle then crystallizes by a solid-state transformation. Such mechanisms are likely to be widespread in solid-state reactions and their characterization will facilitate greater control over these processes.

Synthesis-dependant structural variations in amorphous calcium carbonate

Amorphous calcium carbonate (ACC) was synthesised in the presence of the additives magnesium and poly(aspartic acid) (pAsp) and the structure and crystallisation of these ACC samples was investigated using a range of techniques including X-Ray Absorption Spectroscopy (XAS), X-Ray Diffraction (XRD) and Infra-Red Spectroscopy (IR). The experiments demonstrated that synthetic ACC can be produced with different short-range structures, according to the solution additives used. While the first Mg–ACC precipitates showed short-range structures most similar to aragonite, with monohydrocalcite short-range structures developing with incubation in solution, the initial pAsp–ACC precipitates possessed short-range structures resembling vaterite. The results show that the influence of these additives on the crystallisation of calcium carbonate is apparent even in the precipitation of the first amorphous precursor phase, and that the first stages of recrystallisation involve the expulsion of water from the structure rather than significant changes in the short-range structure around the calcium ions.

Now You See Them

Can new results on calcium carbonate nucleation be reconciled with classical nucleation theory?