Zaklina Burghard

Toughening through nature-adapted nanoscale design

The extraordinary combination of strength and toughness attained by natures highly sophisticated structural design in nacre has inspired the synthesis of novel nanocomposites. In this context, the organic-inorganic hierarchical design of nacre has been mimicked. However, two key features of nacre, namely the scaling of the structural components and the low content of the organic phase, have not been replicated yet. Here, we present thin nanocomposite films with properly adjusted thicknesses of the organic and inorganic layers, as well as a microstructure that closely resembles that of nacre. These films, which are obtained by the combination of low-temperature chemical bath deposition of titania with layer-by-layer assembly of polyelectrolytes, exhibit enhancement in a fracture toughness by a factor of 4, combined with notable increase in hardness, while the Youngs modulus is largely preserved in comparison to the single titania layer. Our findings highlight the significance of the 10:1 inorganic/organic layer thickness ratio evolved by nature, and provide novel perspectives for the future development of efficient bioinspired thin films.

Silicateins—A Novel Paradigm in Bioinorganic Chemistry: Enzymatic Synthesis of Inorganic Polymeric Silica

The inorganic matrix of the siliceous skeletal elements of sponges, that is, spicules, is formed of amorphous biosilica. Until a decade ago, it remained unclear how the hard biosilica monoliths of the spicules are formed in sponges that live in a silica-poor (<50 μM) aquatic environment. The following two discoveries caused a paradigm shift and allowed an elucidation of the processes underlying spicule formation; first the discovery that in the spicules only one major protein, silicatein, exists and second, that this protein displays a bio-catalytical, enzymatic function. These findings caused a paradigm shift, since silicatein is the first enzyme that catalyzes the formation of an inorganic polymer from an inorganic monomeric substrate. In the present review the successive steps, following the synthesis of the silicatein product, biosilica, and resulting in the formation of the hard monolithic spicules is given. The new insight is assumed to open new horizons in the field of biotechnology and also in biomedicine.

Bio-sintering processes in hexactinellid sponges: Fusion of bio-silica in giant basal spicules from Monorhaphis chuni ☆

The two sponge classes, Hexactinellida and Demospongiae, comprise a skeleton that is composed of siliceous skeletal elements (spicules). Spicule growth proceeds by appositional layering of lamellae that consist of silica nanoparticles, which are synthesized via the sponge-specific enzyme silicatein. While in demosponges during maturation the lamellae consolidate to a solid rod, the lamellar organization of hexactinellid spicules largely persists. However, the innermost lamellae, near the spicule core, can also fuse to a solid axial cylinder. Similar to the fusion of siliceous nanoparticles and lamella, in several hexactinellid species individual spicules unify during sintering-like processes. Here, we study the different stages of a process that we termed bio-sintering, within the giant basal spicule (GBS) of Monorhaphis chuni. During this study, a major GBS protein component (27 kDa) was isolated and analyzed by MALDI-TOF-MS. The sequences were used to isolate and clone the encoding cDNA via degenerate primer PCR. Bioinformatic analyses revealed a significant sequence homology to silicatein. In addition, the native GBS protein was able to mediate bio-silica synthesis in vitro. We conclude that the syntheses of bio-silica in M. chuni, and the subsequent fusion of nanoparticles to lamellae, and finally to spicules, are enzymatically-driven by a silicatein-like protein. In addition, evidence is now presented that in hexactinellids those fusions involve sintering-like processes.

Laminates of zinc oxide and poly(amino acid) layers with enhanced mechanical performance

In order to improve the resistance of solution-derived zinc oxide thin films against mechanical stress, nanostructured composite systems of soft organic and brittle ZnO layers were prepared by a bio-inspired process. As the organic component, polyelectrolyte multilayers were prepared by dip-coating using polystyrene sulfonate and poly(amino acids). The organic–inorganic laminates have typical properties in common with nacre: they consist of nanocrystals in a matrix of biomolecules, they exhibit a texture and they proved to be harder than the monolithic mineral.

Hydrogen‐Bond Reinforced Vanadia Nanofiber Paper of High Stiffness

Low-temperature, solution-based self-assembly of vanadia nanofibers yields a free-standing, ceramic paper with an outstanding combination of high strength, stiffness, and macroscopic flexibility. Its excellent mechanical performance results from a brick-and-mortar like architecture, which combines strong covalent bonding within the single-crystalline nanofibers with an intricate hydrogen bonding network between them.

Polymer-derived Si-C-N ceramics reinforced by single wall carbon nanotubes

Abstract Nanocomposites made of polymer-derived Si–C–N ceramic reinforced by single-wall carbon nanotubes (SWCNTs) were prepared for the first time. The synthesis procedure involved ultrasonic dispersion of the nanotubes into a liquid polysilazane precursor polymer, followed by cross-linking and thermolysis. With the aid of nanoindentation testing, dependence of the mechanical properties of the composites on the concentration and agglomeration state of SWCNTs, was studied. The nanotube-filled composites showed improved mechanical performance, as reflected by an increase in Youngs modulus which was found to be correlated with the microstructure of the composites, in particular the degree of dispersion of the nanotubes inside the matrix, whereas the hardness is hardly affected.

Fabrication and characterization of biocompatible nacre-like structures from α-zirconium hydrogen phosphate hydrate and chitosan

Composite materials with an ordered layered structure resembling that of nacre were fabricated by layer-by-layer assembly making use of presynthesized α-zirconium hydrogenphosphate hydrate (ZrP) platelets and chitosan. These two biocompatible materials were chosen in view of possible applications in the biomedical field, e.g., as bone or joint replacement implants. The effect of different concentrations of the inorganic ZrP platelets and the organic components (chitosan) on the composite assembly and structure was investigated. A high concentration of chitosan (0.1 wt.%) resulted in a misalignment of the inorganic platelets, while at very low concentrations (0.001 wt.%), the substrate was not fully covered by the polymer, again leading to misalignment. Also, the concentration of the α-ZrP platelets affected the composite assembly and structure. The number of dipping cycles was varied between 70 and 220, yielding a maximum thickness of approximately 6 μm. The pH value of the chitosan solution was also varied to investigate its influence on the composite assembly. The mechanical properties of the composites were tested with a nanoindenter. For samples prepared with the same number of dipping cycles, higher values of Youngs modulus and hardness were obtained with improved alignment of the platelets in the samples. For samples prepared with 220 dipping cycles, a Youngs modulus of 2.6 GPa and a hardness of 70 MPa were observed. Important general relationships are recognized between the preparation parameters, the degree of order within the nacre-like films and the resulting mechanical properties.

Mesocrystalline calcium silicate hydrate: A bioinspired route toward elastic concrete materials

Controlled aggregation of polymer-stabilized calcium silicate hydrate nanoparticles leads to elastic cementitious materials. Calcium silicate hydrate (C-S-H) is the binder in concrete, the most used synthetic material in the world. The main weakness of concrete is the lack of elasticity and poor flexural strength considerably limiting its potential, making reinforcing steel constructions necessary. Although the properties of C-S-H could be significantly improved in organic hybrids, the full potential of this approach could not be reached because of the random C-S-H nanoplatelet structure. Taking inspiration from a sea urchin spine with highly ordered nanoparticles in the biomineral mesocrystal, we report a bioinspired route toward a C-S-H mesocrystal with highly aligned C-S-H nanoplatelets interspaced with a polymeric binder. A material with a bending strength similar to nacre is obtained, outperforming all C-S-H–based materials known to date. This strategy could greatly benefit future construction processes because fracture toughness and elasticity of brittle cementitious materials can be largely enhanced on the nanoscale.

Cuttlebone-like V 2 O 5 Nanofibre Scaffolds – Advances in Structuring Cellular Solids

The synthesis of ceramic materials combining high porosity and permeability with good mechanical stability is challenging, as optimising the latter requires compromises regarding the first two properties. Nonetheless, significant progress can be made in this direction by taking advantage of the structural design principles evolved by nature. Natural cellular solids achieve good mechanical stability via a defined hierarchical organisation of the building blocks they are composed of. Here, we report the first synthetic, ceramic-based scaffold whose architecture closely mimics that of cuttlebone –a structural biomaterial whose porosity exceeds that of most other natural cellular solids, whilst preserving an excellent mechanical strength. The nanostructured, single-component scaffold, obtained by ice-templated assembly of V2O5 nanofibres, features a highly sophisticated and elaborate architecture of equally spaced lamellas, which are regularly connected by pillars as lamella support. It displays an unprecedented porosity of 99.8 %, complemented by an enhanced mechanical stability. This novel bioinspired, functional material not only displays mechanical characteristics similar to natural cuttlebone, but the multifunctionality of the V2O5 nanofibres also renders possible applications, including catalysts, sensors and electrodes for energy storage.

Piezoelectric Templates - New Views on Biomineralization and Biomimetics.

Biomineralization in general is based on electrostatic interactions and molecular recognition of organic and inorganic phases. These principles of biomineralization have also been utilized and transferred to bio-inspired synthesis of functional materials during the past decades. Proteins involved in both, biomineralization and bio-inspired processes, are often piezoelectric due to their dipolar character hinting to the impact of a template’s piezoelectricity on mineralization processes. However, the piezoelectric contribution on the mineralization process and especially the interaction of organic and inorganic phases is hardly considered so far. We herein report the successful use of the intrinsic piezoelectric properties of tobacco mosaic virus (TMV) to synthesize piezoelectric ZnO. Such films show a two-fold increase of the piezoelectric coefficient up to 7.2 pm V−1 compared to films synthesized on non-piezoelectric templates. By utilizing the intrinsic piezoelectricity of a biotemplate, we thus established a novel synthesis pathway towards functional materials, which sheds light on the whole field of biomimetics. The obtained results are of even broader and general interest since they are providing a new, more comprehensive insight into the mechanisms involved into biomineralization in living nature.