Mesocrystals in Biominerals and Colloidal Arrays

Abstract

Mesocrystals, which originally was a term to designate superstructures of nanocrystals with a common crystallographic orientation, have now evolved to a materials concept. The discovery that many biominerals are mesocrystals generated a large research interest, and it was suggested that mesocrystals result in better mechanical performance and optical properties compared to single crystalline structures. Mesocrystalline biominerals are mainly found in spines or shells, which have to be mechanically optimized for protection or as a load-bearing skeleton. Important examples include red coral and sea urchin spine as well as bones. Mesocrystals can also be formed from purely synthetic components. Biomimetic mineralization and assembly have been used to produce mesocrystals, sometimes with complex hierarchical structures. Important examples include the fluorapatite mesocrystals with gelatin as the structural matrix, and mesocrystalline calcite spicules with impressive strength and flexibility that could be synthesized using silicatein protein fibers as template for calcium carbonate deposition. Self-assembly of nanocrystals can also result in mesocrystals if the nanocrystals have a well-defined size and shape and the assembly conditions are tuned to allow the nanoparticles to align crystallographically. Mesocrystals formed by assembly of monodisperse metallic, semiconducting, and magnetic nanocrystals are a type of colloidal crystal with a well-defined structure on both the atomic and mesoscopic length scale.Mesocrystals typically are hybrid materials between crystalline nanoparticles and interspacing amorphous organic or inorganic layers. This structure allows to combine disparate materials like hard but brittle nanocrystals with a soft and ductile amorphous material, enabling a mechanically optimized structural design as realized in the sea urchin spicule. Furthermore, mesocrystals can combine the properties of individual nanocrystals like the optical quantum size effect, surface plasmon resonance, and size dependent magnetic properties with a mesostructure and morphology tailored for specific applications. Indeed, mesocrystals composed of crystallographically aligned polyhedral or rodlike nanocrystals with anisotropic properties can be materials with strongly directional properties and novel collective emergent properties. An additional advantage of mesocrystals is that they can combine the properties of nanoparticles with a structure on the micro- or macroscale allowing for much easier handling.

Amorphous Phase Mediated Crystallization: Fundamentals of Biomineralization

“…Gower and co-workers have fabricated a variety of non-equilibrium (i.e., non-faceted) morphologies of minerals by using PILP as the precursor, including crystal drops [21], thin films/tablets [62,140,141], and fibers [142,143]. With the help of polyelectrolytes, Cölfen and co-workers have made varied CaC mesocrystals (superstructured nanocrystals with a common crystallographic orientation) (see the review of mesocrystals in biominerals [144]). A mesocrystal can be obtained by the oriented attachment of crystalline precursors [16,[145][146][147].…”

Concerted Growth and Ordering of Cobalt Nanorod Arrays as Revealed by Tandem in Situ SAXS-XAS Studies

“…[37][38][39][66][67][68][69][70][71] It is likely that the already reported examples of some of the superlattices reported to be formed directly in solution are produced by a concerted growth-organization process and constitute similar cases. It has been invoked 36 that polar ligand systems inducing electrostatic interactions could promote the spontaneous formation of supercrystals during growth.…”

TiO2 mesocrystal with nitrogen and fluorine codoping during topochemical transformation: Efficient visible light induced photocatalyst with the codopants

“…It is observed that NFT-500 has a sheet-like structure with {0 0 1} facet dominated from the selective area electron diffusion (SAED) in Fig. 4A inset [19]. Comparable to other samples with different annealing temperatures in Table 1, the EDS analysis of NFT-500 exhibited the high concentrations of N (3.23 wt%) and F (4.87 wt%) in Fig.…”

“…It is inferred that the anisotropic dissolution of NH 4 TiOF 3 can chemically convert to TiO 2 mesocrystal (TMC) during the topochemical transformation, accompanying with N and F releasing [13][14][15][16]. As a new class of porous building blocks oriented assembly of nanocrystals, the obtained TMC with a well-defined crystal shape significantly enhances the charge separation with remarkably long-lived charges and exhibits excellent photocatalytic activities http compared with TiO 2 nanocrystals and commercial P25 [17][18][19][20]. It is a great of significance to introduce the dopant simultaneously from the original precursors or intermedium during the synthesis, without affecting the nucleation and growth of TMC.…”