H. Fabritius

Robustness and optimal use of design principles of arthropod exoskeletons studied by ab initio-based multiscale simulations

Recently, we proposed a hierarchical model for the elastic properties of mineralized lobster cuticle using (i) ab initio calculations for the chitin properties and (ii) hierarchical homogenization performed in a bottom-up order through all length scales. It has been found that the cuticle possesses nearly extremal, excellent mechanical properties in terms of stiffness that strongly depend on the overall mineral content and the specific microstructure of the mineral-protein matrix. In this study, we investigated how the overall cuticle properties changed when there are significant variations in the properties of the constituents (chitin, amorphous calcium carbonate (ACC), proteins), and the volume fractions of key structural elements such as chitin-protein fibers. It was found that the cuticle performance is very robust with respect to variations in the elastic properties of chitin and fiber proteins at a lower hierarchy level. At higher structural levels, variations of design parameters such as the volume fraction of the chitin-protein fibers have a significant influence on the cuticle performance. Furthermore, we observed that among the possible variations in the cuticle ingredients and volume fractions, the experimental data reflect an optimal use of the structural variations regarding the best possible performance for a given composition due to the smart hierarchical organization of the cuticle design.

Structural characterisation of X-ray amorphous calcium carbonate (ACC) in sternal deposits of the crustacea Porcellio scaber

Mineral deposits in land-based woodlice (crustacea, Porcellio scaber) were analysed by high-resolution X-ray diffraction, X-ray absorption spectroscopy (EXAFS) and infrared microscopy. Calcium carbonate is stored within the first four anterior sternites before changing the cuticle (shell). These deposits consist of fully X-ray amorphous calcium carbonate (primary particle size less than 100 A). The short-range order is comparable to crystalline calcium carbonate phases (first coordination shell), but there is increasing structural disorder beyond about 3 A. This high degree of structural disorder gives a high solubility, i.e. an easy mobilisation within the biological system. The results are compared with EXAFS data from the literature on other biogenic amorphous calcium carbonates.

Ab initio study of thermodynamic, structural, and elastic properties of Mg-substituted crystalline calcite.

Arthropoda, which represent nearly 80% of all known animal species, are protected by an exoskeleton formed by their cuticle. The cuticle represents a hierarchically structured multifunctional biocomposite based on chitin and proteins. Some groups, such as Crustacea, reinforce the load-bearing parts of their cuticle with calcite. As the calcite sometimes contains Mg it was speculated that Mg may have a stiffening impact on the mechanical properties of the cuticle (Becker et al., Dalton Trans. (2005) 1814). Motivated by these facts, we present a theoretical parameter-free quantum-mechanical study of the phase stability and structural and elastic properties of Mg-substituted calcite crystals. The Mg-substitutions were chosen as examples of states that occur in complex chemical environments typical for biological systems in which calcite crystals contain impurities, the role of which is still the topic of debate. Density functional theory calculations of bulk (Ca,Mg)CO₃ were performed employing 30-atom supercells within the generalized gradient approximation as implemented in the Vienna Ab-initio Simulation Package. Based on the calculated thermodynamic results, low concentrations of Mg atoms are predicted to be stable in calcite crystals in agreement with experimental findings. Examining the structural characteristics, Mg additions nearly linearly reduce the volume of substituted crystals. The predicted elastic bulk modulus results reveal that the Mg substitution nearly linearly stiffens the calcite crystals. Due to the quite large size-mismatch of Mg and Ca atoms, Mg substitution results in local distortions such as off-planar tilting of the CO₃²⁻ group.

Analysis of CaCO3 deposit formation and degradation during the molt cycle of the terrestrial isopod Porcellio scaber (Crustacea, Isopoda)

Terrestrial isopods store cuticular calcium in large sternal deposits composed of an amorphous CaCO(3) compound. A large part of the deposits consists of numerous small spherules that increase the exposed surface to facilitate resorption of CaCO(3) during cuticle mineralization. It is not known how these spherules are formed and how they are dissolved. This paper presents for the first time an analysis of ultrastructural changes occurring in the sternal CaCO(3) deposits of a terrestrial isopod during their formation and degradation. Our results indicate that formation of the spherules takes place in a specialized aggregation zone, in which 10- to 30-nm-thick granules form agglomerations that then increase in size to form spherules that reveal a concentric growth pattern. Degradation of the deposits occurs in a manner that exposes a maximum of surface area on all levels of their structural organization.

Chitin in the Exoskeletons of Arthropoda: From Ancient Design to Novel Materials Science

The Arthropoda use chitin and various proteins as basic materials of their cuticle which is forming their exoskeletons. The exoskeleton is composed of skeletal elements with physical properties that are adapted to their function and the eco-physiological strains of the animal. These properties are achieved by forming elaborate microstructures that are organized in several hierarchical levels like the so-called twisted plywood structure, which is built by stacks of planar arrays of complex chitin-protein fibres. Additionally, the properties are influenced by variations in the chemical composition of the cuticle, for instance by combining the organic material with inorganic nano-particles. From a materials science point of view, this makes the cuticle to a hierarchical composite material of high functional versatility. The detailed investigation of microstructure, chemical composition and mechanical properties of cuticle from different skeletal elements of the crustacean Homarus americanus shows that cuticle can combine different design principles to create a high-performance anisotropic material. Numerical modelling of the cuticle using ab initio and multiscale approaches even enables the study of mechanical properties on hierarchical levels where experimental methods can no longer be applied. Understanding and eventually applying the underlying design principles of cuticle bears the potential for realization of a completely new generation of man-made structural materials.

Modification of pineapple leaf fibers and graft copolymerization of acrylonitrile onto modified fibers

Raw pineapple leaf fibers (PALFs) were chemically modified by scouring, NaOH treatment, and bleaching (NaClO2). The graft copolymerization of synthetic acrylonitrile monomer onto bleached PALFs was carried out in aqueous medium using potassium persulfate (K2S2O8/FeSO4) as a redox initiator. The maximum grafting level at optimum conditions, namely, monomer concentration, initiator concentration, catalyst concentration, reaction time, and temperature have been determined. The main objective of this study is to decrease the amorphous region of lignocellulose in PALFs and improve its hydrophobic nature by incorporation of synthetic polymer of polyacrylonitrile and mechanical properties. The modified and grafted fibers were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis, and X-ray diffraction study techniques. The moisture content and tensile strength properties were also evaluated for their environmental and mechanical performances.

From insect scales to sensor design: modelling the mechanochromic properties of bicontinuous cubic structures

Many of the three-dimensional photonic crystals occurring in the scales of insects have bicontinuous cubic structures. Their optical properties have been studied extensively, however little is known about their mechanical properties and their optical response under deformation. We demonstrated a mechanochromic effect by deforming the scales of a weevil and calculated the elastic, optical and mechanochromic (assuming homogeneous deformation) properties of the three types of bicontinuous cubic structures occurring in nature: P-structure (primitive), G-structure (gyroid) and D-structure (diamond). The results show that all investigated properties of these three structure types strongly depend on their geometry, structural parameters such as volume fractions of the two constituting phases and the directions of the incident light or applied stress, respectively. Interestingly, the mechanochromic simulation results predict that these structures may show blue-shift or even red-shift under compression along certain directions. Our results provide design guidelines for mechanochromic sensing materials operating in the elastic regime, including parameters such as sensitivity and direction of spectral shift.

Reply to the ‘Comments on “Dental lessons from past to present: ultrastructure and composition of teeth from plesiosaurs, dinosaurs, extinct and recent sharks”’ by H. Botella et al., RSC Adv., 2016, 6, 74384–74388

The structure and composition of 13 fossilized tooth and bone samples aged between 3 and 70 million years were analysed. It was found that they all contained high amounts of fluoroapatite. This indicates that originally present hydroxyapatite had been converted to fluoroapatite during the diagenesis. Thus, the chemical analysis allows no conclusion with respect to the original composition of our fossil samples. Our results indicate that the diagenetic transformation of hydroxyapatite into fluoroapatite is at least partially dependent on microstructural characteristics of the original tissue such as the degree of porosity.