Biominerals exhibit morphologies, hierarchical ordering and properties that invariably surpass those of their synthetic counterparts. A key feature of these materials, which sets them apart from synthetic crystals, is their nanocomposite structure, which derives from intimate association of organic molecules with the mineral host. We here demonstrate the production of artificial biominerals where single crystals of calcite occlude a remarkable 13 wt% of 20 nm anionic diblock copolymer micelles, which act as 'pseudo-proteins'. The synthetic crystals exhibit analogous texture and defect structures to biogenic calcite crystals and are harder than pure calcite. Further, the micelles are specifically adsorbed on {104} faces and undergo a change in shape on incorporation within the crystal lattice. This system provides a unique model for understanding biomineral formation, giving insight into both the mechanism of occlusion of biomacromolecules within single crystals, and the relationship between the macroscopic mechanical properties of a crystal and its microscopic structure.
Organisms have the ability to produce structures with superior characteristics as in the course of biomineralization. One of the most intriguing characteristics of biominerals is the existence of intracrystalline macromolecules.Despite several studies over the last two decades and efforts to mimic the incoporation of macromolecules synthetically, a fundamental understanding of the mechanism of incorporation is as yet lacking. For example, which of the common 20 amino acids are really responsible for the interaction with the mineral phase? Here a reductionist approach, based on high-resolution synchrotron powder diffraction and analytical chemistry, is utilized to screen all of these amino acids in terms of their incorporation into calcite. We showed that the important factors are amino-acid charge, size, rigidity and the relative pKa of the carboxyl and amino functional groups. It is also demonstrated that cysteine, surprisingly, interacts very strongly with the mineral phase and therefore, like acidic amino acids, becomes richly incorporated. The insights gained from this study shed new light on the incorporation of organic molecules into an inorganic host in general, and in particular on the biomineralization process.
Ultraflat metal surfaces are used in template stripping (TS), which is a method for obtaining a metal with an average surface roughness on the order of <1 nm. This is important for plasmonics, for the production of high-quality SAM surfaces, and for many other applications. Herein we show for the first time that TS indeed introduces a very high density of surface nanodefects (twinning and stacking faults), which can strongly hinder surface-induced properties such as SAM ordering and plasmonic phenomena, despite the seemingly overall ultrahigh flatness. We have used state of the art characterization techniques such as HRXRD, spherical-aberration-corrected HRTEM, and STM. We also demonstrate how these nanodefects can be completely eliminated.
We report on the self-formation of periodic atomic and nano steps at the interface between the metal thin film and the underlying supporting substrate, revealed by the template stripping method. Such vicinal-like and atomic stepped surfaces of metals and semiconductors exhibit well-arranged, periodic atomic steps and have numerous applications in microelectronics, catalysis, direction of nanowire arrays, patterning of quantum dots and magnetic domains, and many more. In contrast to classical vicinal surfaces which are produced by the expensive and tedious procedure in which single crystals of a desired material are cut at a small angle to the low surface energy plane followed by surface sputtering and annealing under ultrahigh vacuum for imaging, our surfaces form on polycrystalline materials, at almost room temperature, and at atmospheric environments and have no need of any other procedure in order to image. We also demonstrate how the step periodicity can be easily controlled.
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