Biomineralization is the process by which living organisms orchestrate the synthesis and organization of minerals (biominerals), and it may be viewed as an ancient process for accumulation of metal ions in living systems. The structure and properties of biominerals have yet to be rivaled by any synthetic effort by scientists to date. Therefore, deciphering the assembly algorithms and the components that initiate and promote hierarchical deposition of cations has significant implications for the development of nanocomposites and nanotechnology as a whole. This issue of MRS Bulletin highlights some of the challenges in characterizing and replicating the biomineralization processes, and the role of non-collagenous proteins in the biomineralization process.

This article addresses recent advances in the application of microscopy techniques to characterize crystallization processes as they relate to biomineralization and bioinspired materials synthesis. In particular, we focus on studies aimed at revealing the role organic macromolecules and functionalized surfaces play in modulating the mechanisms of nucleation and growth. In nucleation studies, we explore the use of methods such as in situ transmission electron microscopy, atomic force microscopy, and cryogenic electron microscopy to delineate formation pathways, phase stabilization, and the competing effects of free energy and kinetic barriers. In growth studies, we emphasize understanding the interactions of macromolecular constituents with growing crystals and characterization of the internal structures of the resulting composite crystals using techniques such as electron tomography, atom probe tomography, and vibrational spectromicroscopy. Examples are drawn from both biological and bioinspired synthetic systems.

Biomineralization is the matrix-directed calcification of tissue in living organisms. The deposition of different polymorphs of calcium phosphate or calcium carbonate is a highly regulated process. It may involve cell-controlled mechanisms with vesicular delivery of inorganic material to the extracellular matrix and cell-independent processes mediated by dedicated matrix proteins. These proteins promote the formation of microscopic crystals of defined size and shape, which combine to form bio-inorganic materials with unique properties. Successful biomineralization is correlated with structural elements, such as matrix proteins involved in the nucleation process. Circular dichroism (CD) is a spectroscopic technique for the determination of a secondary structure of proteins and has therefore been applied for studying numerous biomineralization promoter proteins. This article reviews and compares CD data on matrix proteins from different contexts, such as eggs, seashells, and teeth. It highlights the potential of CD for secondary structure determination and quantification and points out pitfalls that may lead to misinterpretation of CD spectra. The data suggest that most biomineralization promoter proteins contain domains of different secondary structure with predominantly unordered conformation. However, they may acquire a higher degree of order initiated by environmental factors such as pH, presence of cations, or charged surfaces.

Modern materials design is largely based on composite structures aimed at a synergistic integration of multiple components with a diverse range of properties. Biologically grown minerals provide an intriguing example of sophisticated organic–inorganic nanocomposite structures resulting in excellent mechanical characteristics. Among the mineral phases utilized by living organisms to generate hard tissues, calcium carbonate—especially the calcite polymorph—is ubiquitous and has been studied intensively. Biogenic calcite crystals often show hierarchical organization spanning multiple length scales, and the occluded organic phases are now known to be intimately associated with the mineral host. Here, we discuss the internal micro- and nanostructure of two selected types of calcite biominerals—the sea urchin spine and prismatic single crystals extracted from mollusk shells. This article highlights recent advances in translating the key principles of biological mineralization into design strategies for synthetic materials and presents analogies between biogenic and synthetic calcite single crystals.

Several organisms possess a genetic program enabling them to form a mineral, a process termed biomineralization. The structure and composition of biominerals equip the biomineralizing organisms with functionalities that abiotic materials made of the same mineral do not necessarily possess. Even primary organisms such as bacteria are able to produce materials with properties superior to those of human-made equivalents. Magnetotactic bacteria represent a paradigm of such microorganisms. These organisms synthesize a hierarchical one-dimensional magnetic nanostructure based on the alignment of magnetosomes—organelles embedded in a vesicle dedicated to biomineralization and made of magnetic nanoparticles (magnetite (Fe3O4) or greigite (Fe3S4)). This article focuses on factors that play a role in the organization of these magnetosomes. The chains, which are based on aligned particles that have biologically controlled ultrastructure, size, morphology, organization, and orientation, serve as actuators and area means to align the bacteria with the Earth’s magnetic field lines when they swim in search of particular habitats in the aqueous environments they live in.

It has been about a hundred years since the atomic nature of matter began to be generally accepted. By the late 1920s, atomic theory was well established, and quantum theory had explained many properties of atoms in gases. The interpretation of the sharp lines in atomic optical spectra could be explained in terms of transitions between electronic energy levels. The application of interacting atoms in solids appeared straightforward in principle, and although quantum theory answered many fundamental questions about condensed matter, theoretical applications were mostly appropriate for idealized models of solids. Because the optical spectra of solids had broad structure, explaining their origin in terms of electronic transitions was more difficult than for the case of atoms. It was not until the 1960s that accurate electronic band structures could be calculated for bulk materials. Basic and applied research involving semiconductors, superconductors, and nanostructured materials has guided the application of quantum theory to condensed matter. These are areas where the use of quantum theory has been central in explaining and predicting properties and has even led to the discovery of new materials.