Boaz Pokroy

Self-organization of a mesoscale bristle into ordered, hierarchical helical assemblies.

Mesoscale hierarchical helical structures with diverse functions are abundant in nature. Here we show how spontaneous helicity can be induced in a synthetic polymeric nanobristle assembling in an evaporating liquid. We use a simple theoretical model to characterize the geometry, stiffness, and surface properties of the pillars that favor the adhesive self-organization of bundles with pillars wound around each other. The process can be controlled to yield highly ordered helical clusters with a unique structural hierarchy that arises from the sequential assembly of self-similar coiled building blocks over multiple length scales. We demonstrate their function in the context of self-assembly into previously unseen structures with uniform, periodic patterns and controlled handedness and as an efficient particle-trapping and adhesive system.

Bacterial biofilm shows persistent resistance to liquid wetting and gas penetration

Most of the world’s bacteria exist in robust, sessile communities known as biofilms, ubiquitously adherent to environmental surfaces from ocean floors to human teeth and notoriously resistant to antimicrobial agents. We report the surprising observation that Bacillus subtilis biofilm colonies and pellicles are extremely nonwetting, greatly surpassing the repellency of Teflon toward water and lower surface tension liquids. The biofilm surface remains nonwetting against up to 80% ethanol as well as other organic solvents and commercial biocides across a large and clinically important concentration range. We show that this property limits the penetration of antimicrobial liquids into the biofilm, severely compromising their efficacy. To highlight the mechanisms of this phenomenon, we performed experiments with mutant biofilms lacking ECM components and with functionalized polymeric replicas of biofilm microstructure. We show that the nonwetting properties are a synergistic result of ECM composition, multiscale roughness, reentrant topography, and possibly yet other factors related to the dynamic nature of the biofilm surface. Finally, we report the impenetrability of the biofilm surface by gases, implying defense capability against vapor-phase antimicrobials as well. These remarkable properties of B. subtilis biofilm, which may have evolved as a protection mechanism against native environmental threats, provide a new direction in both antimicrobial research and bioinspired liquid-repellent surface paradigms.

Vaterite Crystals Contain Two Interspersed Crystal Structures

Double Vision Vaterite is the least stable form of anhydrous crystalline calcium carbonate. While rarely found in geological contexts, it is an important biological precursor and occurs as a minor component in the shells of some organisms. The crystal structure of vaterite has long been debated with no model able to explain all the experimentally observed diffraction spots. Kabalah-Amitai et al. (p. 454) show that vaterite contains two coexisting crystallographic structures that form a pseudo-single crystal. Electron microscopy reveals that vaterite, a calcium carbonate polymorph, comprises at least two distinct crystal structures. Calcite, aragonite, and vaterite are the three anhydrous polymorphs of calcium carbonate, in order of decreasing thermodynamic stability. Although vaterite is not commonly found in geological settings, it is an important precursor in several carbonate-forming systems and can be found in biological settings. Because of difficulties in obtaining large, pure, single crystals, the crystal structure of vaterite has been elusive for almost a century. Using aberration-corrected high-resolution transmission electron microscopy, we found that vaterite is actually composed of at least two different crystallographic structures that coexist within a pseudo–single crystal. The major structure exhibits hexagonal symmetry; the minor structure, existing as nanodomains within the major matrix, is still unknown.

On the structure of aragonite

High-resolution synchrotron powder diffraction measurements were carried out at the 32-ID beamline of the Advanced Photon Source of Argonne National Laboratory in order to clarify the structure of geological aragonite, a widely abundant polymorph of CaCO(3). The investigated crystals were practically free of impurity atoms, as measured by wavelength-dispersive X-ray spectroscopy in scanning electron microscopy. A superior quality of diffraction data was achieved by using the 11-channel 111 Si multi-analyzer of the diffracted beam. Applying the Rietveld refinement procedure to the high-resolution diffraction spectra, we were able to extract the aragonite lattice parameters with an accuracy of about 20 p.p.m. The data obtained unambiguously confirm that pure aragonite crystals have orthorhombic symmetry.

Control of shape and size of nanopillar assembly by adhesion-mediated elastocapillary interaction.

Control of self-organization of nanofibers into regular clusters upon evaporation-induced assembly is receiving increasing attention due to the potential importance of this process in a range of applications including particle trapping, adhesives, and structural color. Here we present a comprehensive study of this phenomenon using a periodic array of polymeric nanopillars with tunable parameters as a model system to study how geometry, mechanical properties, as well as surface properties influence capillary-induced self-organization. In particular, we show that varying the parameters of the building blocks of self-assembly provides us with a simple means of controlling the size, chirality, and anisotropy of complex structures. We observe that chiral assemblies can be generated within a narrow window for each parameter even in the absence of chiral building blocks or a chiral environment. Furthermore, introducing anisotropy in the building blocks provides a way to control both the chirality and the size of the assembly. While capillary-induced self-assembly has been studied and modeled as a quasi-static process involving the competition between only capillary and elastic forces, our results unequivocally show that both adhesion and kinetics are equally important in determining the final assembly. Our findings provide insight into how multiple parameters work together in capillary-induced self-assembly and provide us with a diverse set of options for fabricating a variety of nanostructures by self-assembly.

Microstructure of natural plywood-like ceramics: a study by high-resolution electron microscopy and energy-variable X-ray diffraction

The three-dimensional microstructure of a Strombus decorus persicus seashell was studied by means of high-resolution electron microscopy and energy-variable X-ray diffraction on synchrotron beam lines. Energy variation in small steps allows the X-ray penetration depth to be changed precisely and, on this basis, for a non-destructive microstructural analysis with depth resolution to be developed. This technique enabled determination of depth-resolved microstructural parameters, such as the degree of the preferred orientation, the lamella size, and average microstrain fluctuations in both the prismatic and the crossed-lamellar layers of these seashells. The X-ray results were in good agreement with direct observations made by electron microscopy. A detailed study of the shell microstructure shed additional light on the relationship between the structural characteristics and superior mechanical properties of seashells.

Tuning hardness in calcite by incorporation of amino acids

Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit-mineral single crystals containing embedded macromolecules-remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.

Bio‐Inspired Band Gap Engineering of Zinc Oxide by Intracrystalline Incorporation of Amino Acids

Bandgap engineering of zinc oxide semiconductors can be achieved using a bio-inspired method. During a bioInspired crystallization process, incorporation of amino acids into the crystal structure of ZnO induces lattice strain that leads to linear bandgap shifts. This allows for fine tuning of the bandgap in a bio-inspired route.

Biomineralization of calcium carbonate: structural aspects

We analyze the observed structural distinctions between calcium carbonate crystals of biogenic and non-biogenic origin in terms of interaction between organic macromolecules and growing mineral. We conclude that rather strong forces are imposed by organic macromolecules on mineral crystallites, which cause lattice strains of about 0.2%. According to the developed model, these strains arise primarily throughout the amorphous-crystalline phase transformation at early stages of biomineralization.

Protein-induced, previously unidentified twin form of calcite

Using single-crystal x-ray diffraction, we found a formerly unknown twin form in calcite crystals grown from solution to which a mollusc shell-derived 17-kDa protein, Caspartin, was added. This intracrystalline protein was extracted from the calcitic prisms of the Pinna nobilis shells. The observed twin form is characterized by the twinning plane of the (108)-type, which is in addition to the known four twin laws of calcite identified during 150 years of investigations. The established twin forms in calcite have twinning planes of the (001)-, (012)-, (104)-, and (018)-types. Our discovery provides additional evidence on the crucial role of biological macromolecules in biomineralization.