Anna S. Schenk

Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate

Despite its importance in many industrial, geological and biological processes, the mechanism of crystallization from supersaturated solutions remains a matter of debate. Recent discoveries show that in many solution systems nanometre-sized structural units are already present before nucleation. Still little is known about the structure and role of these so-called pre-nucleation clusters. Here we present a combination of in situ investigations, which show that for the crystallization of calcium phosphate these nanometre-sized units are in fact calcium triphosphate complexes. Under conditions in which apatite forms from an amorphous calcium phosphate precursor, these complexes aggregate and take up an extra calcium ion to form amorphous calcium phosphate, which is a fractal of Ca(2)(HPO(4))(3)(2-) clusters. The calcium triphosphate complex also forms the basis of the crystal structure of octacalcium phosphate and apatite. Finally, we demonstrate how the existence of these complexes lowers the energy barrier to nucleation and unites classical and non-classical nucleation theories.

A critical analysis of calcium carbonate mesocrystals.

The term mesocrystal has been widely used to describe crystals that form by oriented assembly, and that exhibit nanoparticle substructures. Using calcite crystals co-precipitated with polymers as a suitable test case, this article looks critically at the concept of mesocrystals. Here we demonstrate that the data commonly used to assign mesocrystal structure may be frequently misinterpreted, and that these calcite/polymer crystals do not have nanoparticle substructures. Although morphologies suggest the presence of nanoparticles, these are only present on the crystal surface. High surface areas are only recorded for crystals freshly removed from solution and are again attributed to a thin shell of nanoparticles on a solid calcite core. Line broadening in powder X-ray diffraction spectra is due to lattice strain only, precluding the existence of a nanoparticle sub-structure. Finally, study of the formation mechanism provides no evidence for crystalline precursor particles. A re-evaluation of existing literature on some mesocrystals may therefore be required.

Three-dimensional imaging of dislocation propagation during crystal growth and dissolution

Atomic level defects such as dislocations play key roles in determining the macroscopic properties of crystalline materials 1,2. Their effects range from increased chemical reactivity 3,4 to enhanced mechanical properties 5,6. Dislocations have been widely studied using traditional techniques such as X-ray diffraction and optical imaging. Recent advances have enabled atomic force microscopy to study single dislocations 7 in two-dimensions (2D), while transmission electron microscopy (TEM) can now visualise strain fields in three-dimensions (3D) with near atomic resolution 8–10. However, these techniques cannot offer 3D imaging of the formation or movement of dislocations during dynamic processes. Here, we describe how Bragg Coherent Diffraction Imaging (BCDI) 11,12 can be used to visualize in 3D, the entire network of dislocations present within an individual calcite crystal during repeated growth and dissolution cycles. These investigations demonstrate the potential of BCDI for studying the mechanisms underlying the response of crystalline materials to external stimuli.

Polymer-induced liquid precursor (PILP) phases of calcium carbonate formed in the presence of synthetic acidic polypeptides—relevance to biomineralization

Polymer-induced liquid precursor (PILP) phases of calcium carbonate have attracted significant interest due to possible applications in materials synthesis, and their resemblance to intermediates seen in biogenic mineralisation processes. Further, these PILP phases have been formed in vitro using polyelectrolytes such as poly(aspartic acid) which bears many structural parallels to the highly acidic biomacromolecules that are associated with biogenic calcium carbonate. This article describes experiments which investigate how the composition of acidic polypeptides determines their ability to form PILP phases of CaCO3, and therefore whether it is feasible that the acidic biomacromolecules extracted from CaCO3 biominerals could also function in this way. A series of random copoly(amino acid)s constructed from 80–20%, 50–50% and 20–80% aspartic acid and serine residues were synthesised and their effect on CaCO3 precipitation was determined. A strong correlation between the composition and function of the polypeptide was observed. Only the polypeptide containing 80% aspartic acid residues (Asp80%–Ser20%) induced the formation of continuous CaCO3 films, which provide a fingerprint of an intermediary PILP phase, while addition of Mg2+ also facilitated the formation of expanded film-like structures with the polypeptide Asp50%–Ser50%. In contrast, the weakly-acidic polypeptide Asp20%–Ser80% had only a minor effect on the crystal morphologies and also failed to aid infiltration of CaCO3 into small pores. These results therefore demonstrate that counter-ion induced phase separation of highly acidic biomacromolecules proteins appears to be entirely feasible based upon their composition, but that evidence for the operation of this mineralisation mechanism in vivo is still required.

Sonication-Assisted Synthesis of Large, High-Quality Mercury Thiolate Single Crystals Directly from Liquid Mercury

The synthetic formation of mercury thiolates has been known for almost 200 years. These compounds are usually formed by a slow reaction of mercury salts with thiolates or disulfides to produce small (up to 1 μm), plate-like crystals of Hg(S-R)(2). Herein we show that such mercury thiolates can be formed directly from liquid mercury via sonication with neat thiols. The process not only produces crystals very rapidly (within seconds) but also leads to the formation of large crystals (up to hundreds of micrometers). The high quality of these crystals enabled their detailed structural characterization, which showed that the crystals are composed of ordered Hg(thiol)(2) stacks. We extended the experimental procedure to form and characterize a range of Hg thiolate crystals with various chain lengths. We propose a new self-assembly mechanism that can explain how sonication--which is usually used to break chemical bonds, to disperse materials, and to form nanosized crystallites--may lead to the growth of large, high-quality crystals.

Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.