Breaking the long-standing morphological paradigm: Individual prisms in the pearl oyster shell grow perpendicular to the c-axis of calcite.

Cross-sections of calcitic prismatic layers in mollusk shells, cut perpendicular to growth direction, reveal well-defined polygonal shapes of individual "grains" clearly visible by light and electron microscopy. For several kinds of shells, it was shown that the average number of edges in an individual prism approaches six during the growth process. Taking into account the rhombohedral symmetry of calcite, often presented in hexagonal axes, all this led to the long-standing opinion that calcitic prisms grow along the c-axis of calcite. In this paper, using X-ray diffraction and electron backscatter diffraction (EBSD), we unambiguously show that calcitic prisms in pearl oyster Pinctada margaritifera predominantly grow perpendicular to the c-axis. The obtained results imply that the hexagon-like habitus of growing crystallites may be not necessarily connected to calcite crystallography and, therefore, other factors should be taken into consideration. We analyze this phenomenon by comparing the organic contents in Pinctada margaritifera and Pinna nobilis shells, the later revealing regular growth of calcitic prisms along the c-axis.

Structure and composition of Unio pictorum shell: arguments for the diversity of the nacroprismatic arrangement in molluscs.

Mollusc shells are complex organomineral structures, the arrangement and composition depending on the species. Most studies are dedicated to shells composed of an aragonite nacreous and a calcite prismatic layer, so the nacreous prismatic model based on Pinctada and Atrina-Pinna. Here, we studied the micro- and nanostructure, the mineralogy and composition of a nacroprismatic bivalve species: Unio pictorum. The prismatic layer of Unio is aragonite, and the inner structure of the prismatic units strongly differs from those of the calcitic layers. The shape of the prisms varies depending on their growth stage. The first layers of nacre are similar to those of gastropods (columnar nacre), then evolve towards the typical bivalve arrangement (sheet nacre). Na, Sr, Mg, P and S are present in both prisms and nacre. The organic prismatic envelopes are rich in sulphur amino acids, whereas organic sulphate is present within the prisms and the nacreous tablets. P is present as phosphate, probably a mixture of organic and mineral complex. Chemical distribution maps confirm the absence of an organic membrane between the nacre and the prisms. The comparison of the structure, mineralogy and composition of Unio pictorum and different species show the diversity of nacroprismatic shells, and that these features are taxonomically dependent.

A computational study on the role of noncovalent interactions in the stability of polymer/graphene nanocomposites.

Understanding the interaction between graphene and polymers is of essential interest when designing novel nanocomposites with reinforced mechanical and electrical properties. In this computational study, the interaction of pristine graphene (PG) and graphene oxide (GO) with a series of functional groups, representative of the functionalised buildings blocks occurring in different polymers, and attached to aliphatic and aromatic chains, is analyzed using dispersion-corrected semi-empirical methods (PM6-D3H4X) and density functional theory calculations with empirical dispersion corrections. Functional groups include alkyl, hydroxyl, aldehyde, carboxyl, amino and nitro groups, and the binding energies of these groups with graphene derivatives (PG and GO) are determined. Nitro- and carbonyl groups display stronger interactions in both aliphatic and aromatic chains. The importance of dispersion-type and non-covalent interactions (NCI) in general, which typically, double the interaction energies, is revealed. The results are interpreted in an extensive NCI analysis in order to characterize the different types of NCI, providing a better understanding of the nature of the interaction (π-π stacking, CH-π bonding, H-bonding and lone pair-π interaction) at stake. In order to highlight the influence of polymer structure/conformation on top of that of their functional groups, the binding of three polymers, polyethylene (PE), polystyrene (PS) and polyvinylidene fluoride (PVDF), on pristine graphene is also investigated. Our calculations indicate that, although all polymers exhibit evident attractive interactions with the graphene sheet, the overall interaction is strongly influenced by the specific polymer structure. Thus, three main conformations of PVDF (the so-called α, ß and γ, ε conformations) are analyzed and we find that, although the α-conformer with a trans-gauche-trans-gauche (TGTG') conformation is the lowest energy conformer, the ß-conformation of PVDF with the hydrogen atoms facing the graphene ("F-up") has the strongest interaction with the graphene surface among the polymers under consideration. Taken together, our computational approach sheds light on the character and importance of non-covalent graphene-polymer functional group interactions combined with the structural/conformational properties of the polymer, which are at stake in the design of novel nanocomposites with reinforced mechanical and electrical properties.

Identifying predation on rodent teeth through structure and composition: A case from Morocco.

Predation by nocturnal birds of prey is one of the most frequent modes leading to the concentration of rodents in fossil assemblages. This mode of accumulation leaves characteristic surface alterations on bones and teeth. In order to evaluate and characterize the effects of these pre-diagenesis alterations on rodent fossil samples, we have carried out microstructural and chemical analyses on incisors collected from present day Moroccan wild animals and owl pellets. The microstructure of both dentine and enamel was well preserved, but chemical changes were evident in pellet samples and depended on the particular tissue and the nature of the predator. The comparison of compositional data obtained from electron microprobe chemical analyses and infrared spectrometry has allowed us to assign a possible predator to an incisor extracted from a pellet of an unknown origin. This method has further implications for the understanding of taphonomy and palaeoecology of archaeological and fossil sites.

A layered structure in the organic envelopes of the prismatic layer of the shell of the pearl oyster Pinctada margaritifera (Mollusca, Bivalvia).

The organic interprismatic layers of the mollusc Pinctada margaritifera are studied using a variety of highly spatially-resolved techniques to establish their composition and structure. Our results show that both the interlamellar sheets of the nacre and interprismatic envelopes form layered structures. Additionally, these organic layers are neither homogeneous in composition, nor continuous in their structure. Both structures play a major role in the biomineralization process and act as a boundary between mineral units.

Lipids from the nacreous and prismatic layers of two Pteriomorpha mollusc shells.

Mollusc shells are acellular biominerals, in which macromolecular structures are intimately associated with mineral phases. Most studies are devoted to proteins, despite sugars have been described. Lipids were extracted from the calcite prismatic and aragonite nacreous layer of two mollusc shells. Fourier Transform Infrared Spectrometry shows that lipids are present in both samples, but they are not similar. Thin layer chromatography confirms that lipids are different in the two studied layers, so that it may be suggested they are species-dependant. Although not yet deciphered, their role in biomineralization and fossilisation processes is probably important.

Multiscale structure of calcite fibres of the shell of the brachiopod Terebratulina retusa.

The shells of rhynchonelliform brachiopods have an outer (primary) layer of acicular calcite and an inner (secondary) layer of calcite fibres which are parallel to the shell exterior. Atomic force microscopy (AFM) reveals that these fibres are composed of large triangular nanogranules of about 600-650 nm along their long axis. The nanogranules are composites of organic and inorganic components. As the shell grows, the fibres elongate with the calcite c-axis perpendicular to the fibre axis as demonstrated by electron backscatter diffraction (EBSD). Thus, despite being a composite structure comprising granules that are themselves composites, each fibre is effectively a single crystal. The combination of AFM and EBSD reveals the details of the structure and crystallography of these fibres. This knowledge serves to identify those aspects of biological control that must be understood to enable comprehension of the biological control exerted on the construction of these exquisite biomineral structures.

Composition and properties of the soluble organic matrix of the otolith of a marine fish: Gadus morhua Linne, 1758 (Teleostei, Gadidae).

The soluble matrix of the sagittal otolith of the cod Gadus morhua was analyzed using UV and IR spectroscopy, liquid chromatography and electrophoresis. This matrix is a complex mixture of proteins and glycoproteins, with a large range of molecular weights. High weights (>1000 kDa) are shown for the first time in water-soluble matrix of otolith. However, the 2D denaturing electrophoresis and large range of sorting used in high performance liquid chromatography columns do not separate the soluble matrix to well-defined molecular weights. The IR data indicate that several conformations are present and the main part of the sugars is not sulfated. Additionally, electrophoresis data show that the acidity of the sugar components is higher than that of the proteins. Despite the relative scarcity of literature data, our study of G. morhua suggests that the chemical composition of otolith soluble organic matrix may differ among species.

Comparison of the soluble matrices of the calcitic prismatic layer of Pinna nobilis (Mollusca, Bivalvia, Pteriomorpha).

The calcitic prisms of the outer layer of the shell of Pinna nobilis, surrounded by thick organic walls, contain a soluble intracrystalline matrix. The structure and composition of the outer interprismatic walls are not well known. The current viewpoint is they are composed of an insoluble matrix. Another thick organic structure, the interlamellar sheet of the nacreous layer, is composed of insoluble and soluble matrices. The composition of two sets of soluble organic matrices from the calcitic layer of Pinna nobilis, extracted with and without the organic walls are compared. According to the various analyses (SEM and AFM, UV and FTIR spectrometry, HPLC, electrophoreses, XANES), the main characteristics of the two matrices are similar, but not identical. Thus, the organic walls contain soluble components. However, the three-layered structure of the interlamellar sheet of the nacreous layer has not been observed.

Comparative studies of skeletal soluble matrices from some Scleractinian corals and Molluscs.

The soluble organic matrices extracted from aragonitic skeletons of five Scleractinia and two Molluscs were analyzed using FTIR spectrometry, HPLC and 2-D gel electrophoresis. All these methods show that scleractinian and molluscan matrices are different. Both matrices are acidic with poorly separated molecular weights. The scleractinian matrices are highly glycosylated, whereas the molluscan matrices are not as shown by stains in 2D-electrophoresis. These results were in accordance with earlier data: high S contents in Scleractinia skeletons and low S contents in Mollusca shells. These results confirm the control of the morphology and the chemical composition of aragonite biocrystals in various taxa.

Structure and composition of the aragonitic crossed lamellar layers in six species of Bivalvia and Gastropoda.

The microstructures, the chemical composition and the soluble organic matrices of the aragonitic crossed lamellar layers of the shells of six species of molluscs have been studied. The microstructures and chemical contents are similar, whereas the quantities of organic matrices are variable. All the soluble matrices are glycoproteins, with low S contents. Their molecular weights, the protein-sugar ratios and acidities are variable. Neither a gastropod nor a bivalve pattern is recognized. The diversity of the organic matrices probably plays a main role in the fossilization processes of mollusc shells.

Comparison of the soluble organic matrices of healthy and diseased shells of Pinctada margaritifera (L.) and Pecten maximus L. (Mollusca, Bivalvia).

Pinctada margaritifera and Pecten maximus are among the mollusks of commercial value. Both are known to show abnormal calcification processes that strongly increase the mortality rate. Several parameters of the soluble organic matrices extracted from the shells of P. margaritifera and P. maximus are analyzed: bulk composition, molecular weights, and acidity. The composition of the matrices of healthy and diseased shells were compared, showing that the protein and the sugar contents are variously modified. Differences between healthy and diseased shells are dissimilar in the two species. This is in accordance with the previously described macroscopic and microscopic alterations (red color, numerous brown membranes). This study does not allow identification the origin of the disease, but provides new insights on the role of sugars in biomineralization processes.

Taphonomy and palaeoecology of Olduvai Bed-I (Pleistocence, Tanzania).

Detailed taxonomic and taphomonic studies of rodents and palaeoecological analysis have been undertaken to investigate faunal change in Olduvai Bed-I. The palaeoenvironments inferred from rodent faunas recorded in Olduvai Bed-I suggest a change between the middle (FLK + FLKNN) and the top of the series (FLKN). Changes have also been observed from taxonomic studies of large mammals and from palynological studies. These differences have been attributed in the past to climatic change, but taphonomic studies suggest a more complex scenario. The environment at Olduvai Bed-I is here interpreted through analysis of fossil faunas and fossilization processes. Identification of the causative agents that could have altered the faunal composition provides information on the environment and on the nature of the change observed between the middle and top of Bed-I. This information can then be used to test conflicting hypotheses about the origins and amount of faunal and pollen change. Results show evidence of predation in all units of Bed-I and can be attributed to different predators along the series. Different predator behaviours explain some of the variability observed by previous authors in the small mammal species composition between the middle and the top of Bed-I. After taking taphonomy into account, the remaining faunal differences point to environmental differences between middle and upper Bed-I and even greater within the upper Bed-I sequence. These differences go beyond the range that is present today in the tropical woodland-savanna biome. Our interpretation of the palaeoenvironments is that the middle Bed-I faunas indicate a very rich closed woodland environment, richer than any part of the present-day savanna biome in Africa, changing to less rich woodland in upper Bed-I with a trend towards more open and seasonal woodlands at the top of the series.

Isoelectric properties of the soluble matrices in relation to the chemical composition of some Scleractinian skeletons.

Soluble matrices of four Scleractinian skeletons (Madrepora, Favia, Leptastrea and Fungia), were extracted and studied by isoelectric focusing (IEF). The main part of the extracted matrices is acidic. IEF gels are poorly stained or unstained by Coomassie Blue and silver. The positive Alcian Blue staining is indicative of a sulfated and acidic nature of the glycoproteins. Chemical analysis shows high S contents in Scleractinian skeletons. These results are supported by the comparison with IEF and chemical contents of Molluscan shells.