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1.  Mechanical properties of nacre and highly mineralized bone. 
We compared the mechanical properties of 'ordinary' bovine bone, the highly mineralized bone of the rostrum of the whale Mesoplodon densirostris, and mother of pearl (nacre) of the pearl oyster Pinctada margaritifera. The rostrum and the nacre are similar in having very little organic material. However, the rostral bone is much weaker and more brittle than nacre, which in these properties is close to ordinary bone. The ability of nacre to outperform rostral bone is the result of its extremely well-ordered microstructure, with organic material forming a nearly continuous jacket round all the tiny aragonite plates, a design well adapted to produce toughness. In contrast, in the rostrum the organic material, mainly collagen, is poorly organized and discontinuous, allowing the mineral to join up to form, in effect, a brittle stony material.
doi:10.1098/rspb.2000.1337
PMCID: PMC1087608  PMID: 12123292
2.  Origin of flaw-tolerance in nacre 
Scientific Reports  2013;3:1693.
Over the past decades, our understanding of nacre's toughening origin has long stayed at the level of crack deflection along the biopolymer interface between aragonite platelets. It has been widely thought that the ceramic aragonite platelets in nacre invariably remain shielded from the propagating crack. Here we report an unexpected experimental observation that the propagating crack, surprisingly, invades the aragonite platelet following a zigzag crack propagation trajectory. The toughening origin of previously-thought brittle aragonite platelet is ascribed to its unique nanoparticle-architecture, which tunes crack propagation inside the aragonite platelet in an intergranular manner. For comparison, we also investigated the crack behavior in geologic aragonite mineral (pure monocrystal) and found that the crack propagates in a cleavage fashion, in sharp contrast with the intergranular cracking in the aragonite platelet of nacre. These two fundamentally different cracking mechanisms uncover a new toughening strategy in nacre's hierarchical flaw-tolerance design.
doi:10.1038/srep01693
PMCID: PMC3631768  PMID: 23603788
3.  Organic–inorganic interfaces and spiral growth in nacre 
Nacre, the crown jewel of natural materials, has been extensively studied owing to its remarkable physical properties for over 160 years. Yet, the precise structural features governing its extraordinary strength and its growth mechanism remain elusive. In this paper, we present a series of observations pertaining to the red abalone (Haliotis rufescens) shell's organic–inorganic interface, organic interlayer morphology and properties, large-area crystal domain orientations and nacre growth. In particular, we describe unique lateral nano-growths and paired screw dislocations in the aragonite layers, and demonstrate that the organic material sandwiched between aragonite platelets consists of multiple organic layers of varying nano-mechanical resilience. Based on these novel observations and analysis, we propose a spiral growth model that accounts for both [001] vertical propagation via helices that surround numerous screw dislocation cores and simultaneous 〈010〉 lateral growth of aragonite sheet structure. These new findings may aid in creating novel organic–inorganic micro/nano composites through synthetic or biomineralization pathways.
doi:10.1098/rsif.2008.0316
PMCID: PMC2572677  PMID: 18753125
nacre; biomineralization; crystal growth
4.  Patterns of Expression in the Matrix Proteins Responsible for Nucleation and Growth of Aragonite Crystals in Flat Pearls of Pinctada fucata 
PLoS ONE  2013;8(6):e66564.
The initial growth of the nacreous layer is crucial for comprehending the formation of nacreous aragonite. A flat pearl method in the presence of the inner-shell film was conducted to evaluate the role of matrix proteins in the initial stages of nacre biomineralization in vivo. We examined the crystals deposited on a substrate and the expression patterns of the matrix proteins in the mantle facing the substrate. In this study, the aragonite crystals nucleated on the surface at 5 days in the inner-shell film system. In the film-free system, the calcite crystals nucleated at 5 days, a new organic film covered the calcite, and the aragonite nucleated at 10 days. This meant that the nacre lamellae appeared in the inner-shell film system 5 days earlier than that in the film-free system, timing that was consistent with the maximum level of matrix proteins during the first 20 days. In addition, matrix proteins (Nacrein, MSI60, N19, N16 and Pif80) had similar expression patterns in controlling the sequential morphologies of the nacre growth in the inner-film system, while these proteins in the film-free system also had similar patterns of expression. These results suggest that matrix proteins regulate aragonite nucleation and growth with the inner-shell film in vivo.
doi:10.1371/journal.pone.0066564
PMCID: PMC3680448  PMID: 23776687
5.  Material properties of brachiopod shell ultrastructure by nanoindentation 
Mineral-producing organisms exert exquisite control on all aspects of biomineral production. Among shell-bearing organisms, a wide range of mineral fabrics are developed reflecting diverse modes of life that require different material properties. Our knowledge of how biomineral structures relate to material properties is still limited because it requires the determination of these properties on a detailed scale. Nanoindentation, mostly applied in engineering and materials science, is used here to assess, at the microstructural level, material properties of two calcite brachiopods living in the same environment but with different modes of life and shell ultrastructure. Values of hardness (H) and the Young modulus of elasticity (E) are determined by nanoindentation. In brachiopod shells, calcite semi-nacre provides a harder and stiffer structure (H∼3–6 GPa; E=60–110/120 GPa) than calcite fibres (H=0–3 GPa; E=20–60/80 GPa). Thus, brachiopods with calcite semi-nacre can cement to a substrate and remain immobile during their adult life cycle. This correlation between mode of life and material properties, as a consequence of ultrastructure, begins to explain why organisms produce a wide range of structures using the same chemical components, such as calcium carbonate.
doi:10.1098/rsif.2006.0150
PMCID: PMC2358955  PMID: 17015292
nanoindentation; brachiopod; biomineral; shell ultrastructure; ecology
6.  Multifunctional, supramolecular, continuous artificial nacre fibres 
Scientific Reports  2012;2:767.
Nature has created amazing materials during the process of evolution, inspiring scientists to studiously mimic them. Nacre is of particular interest, and it has been studied for more than half-century for its strong, stiff, and tough attributes resulting from the recognized “brick-and-mortar” (B&M) layered structure comprised of inorganic aragonite platelets and biomacromolecules. The past two decades have witnessed great advances in nacre-mimetic composites, but they are solely limited in films with finite size (centimetre-scale). To realize the adream target of continuous nacre-mimics with perfect structures is still a great challenge unresolved. Here, we present a simple and scalable strategy to produce bio-mimic continuous fibres with B&M structures of alternating graphene sheets and hyperbranched polyglycerol (HPG) binders via wet-spinning assembly technology. The resulting macroscopic supramolecular fibres exhibit excellent mechanical properties comparable or even superior to nacre and bone, and possess fine electrical conductivity and outstanding corrosion-resistance.
doi:10.1038/srep00767
PMCID: PMC3479450  PMID: 23097689
7.  Ubiquitylation Functions in the Calcium Carbonate Biomineralization in the Extracellular Matrix 
PLoS ONE  2012;7(4):e35715.
Mollusks shell formation is mediated by matrix proteins and many of these proteins have been identified and characterized. However, the mechanisms of protein control remain unknown. Here, we report the ubiquitylation of matrix proteins in the prismatic layer of the pearl oyster, Pinctada fucata. The presence of ubiquitylated proteins in the prismatic layer of the shell was detected with a combination of western blot and immunogold assays. The coupled ubiquitins were separated and identified by Edman degradation and liquid chromatography/mass spectrometry (LC/MS). Antibody injection in vivo resulted in large amounts of calcium carbonate randomly accumulating on the surface of the nacreous layer. These ubiquitylated proteins could bind to specific faces of calcite and aragonite, which are the two main mineral components of the shell. In the in vitro calcium carbonate crystallization assay, they could reduce the rate of calcium carbonate precipitation and induce the calcite formation. Furthermore, when the attached ubiquitins were removed, the functions of the EDTA-soluble matrix of the prismatic layer were changed. Their potency to inhibit precipitation of calcium carbonate was decreased and their influence on the morphology of calcium carbonate crystals was changed. Taken together, ubiquitylation is involved in shell formation. Although the ubiquitylation is supposed to be involved in every aspect of biophysical processes, our work connected the biomineralization-related proteins and the ubiquitylation mechanism in the extracellular matrix for the first time. This would promote our understanding of the shell biomineralization and the ubiquitylation processes.
doi:10.1371/journal.pone.0035715
PMCID: PMC3338455  PMID: 22558208
8.  Uncovering high-strain rate protection mechanism in nacre 
Scientific Reports  2011;1:148.
Under high-strain-rate compression (strain rate ∼103 s−1), nacre (mother-of-pearl) exhibits surprisingly high fracture strength vis-à-vis under quasi-static loading (strain rate 10−3 s−1). Nevertheless, the underlying mechanism responsible for such sharply different behaviors in these two loading modes remains completely unknown. Here we report a new deformation mechanism, adopted by nacre, the best-ever natural armor material, to protect itself against predatory penetrating impacts. It involves the emission of partial dislocations and the onset of deformation twinning that operate in a well-concerted manner to contribute to the increased high-strain-rate fracture strength of nacre. Our findings unveil that Mother Nature delicately uses an ingenious strain-rate-dependent stiffening mechanism with a purpose to fight against foreign attacks. These findings should serve as critical design guidelines for developing engineered body armor materials.
doi:10.1038/srep00148
PMCID: PMC3216628  PMID: 22355664
9.  Liquid crystal self-templating approach to ultrastrong and tough biomimic composites 
Scientific Reports  2013;3:2374.
Materials with both high strength and toughness are in great demand for a wide range of applications, requiring strict design of ingredients and hierarchically ordered architecture from nano- to macro-scale. Nacre achieves such a target in the long natural evolution by alternative alignment of inorganic nanoplatelets and biomacromolecules. To mimic nacre, various strategies were developed, approaching nacre-comparable performance in limited size. How to remarkably exceed nacre in both property and size is a key issue to further the advancement of composites. Here we present liquid crystal self-templating methodology to make the next generation of ultrastrong and tough nacre-mimics continuously. The hierarchically assembled composites show the highest tensile strength (652 MPa) among nacre mimics, five to eight times as high as that of nacre (80–135 MPa), and excellent ductility with toughness of 18 MJ m−3, one to two orders of magnitude greater than that of nacre (0.1 ~ 1.8 MJ m−3).
doi:10.1038/srep02374
PMCID: PMC3734524  PMID: 23918042
10.  Identification of Proteins with Potential Osteogenic Activity Present in the Water-Soluble Matrix Proteins from Crassostrea gigas Nacre Using a Proteomic Approach 
The Scientific World Journal  2012;2012:765909.
Nacre, when implanted in vivo in bones of dogs, sheep, mice, and humans, induces a biological response that includes integration and osteogenic activity on the host tissue that seems to be activated by a set of proteins present in the nacre water-soluble matrix (WSM). We describe here an experimental approach that can accurately identify the proteins present in the WSM of shell mollusk nacre. Four proteins (three gigasin-2 isoforms and a cystatin A2) were for the first time identified in WSM of Crassostrea gigas nacre using 2DE and LC-MS/MS for protein identification. These proteins are thought to be involved in bone remodeling processes and could be responsible for the biocompatibility shown between bone and nacre grafts. These results represent a contribution to the study of shell biomineralization process and opens new perspectives for the development of new nacre biomaterials for orthopedic applications.
doi:10.1100/2012/765909
PMCID: PMC3361287  PMID: 22666151
11.  The dynamics of nacre self-assembly 
We show how nacre and pearl construction in bivalve and gastropod molluscs can be understood in terms of successive processes of controlled self-assembly from the molecular- to the macro-scale. This dynamics involves the physics of the formation of both solid and liquid crystals and of membranes and fluids to produce a nanostructured hierarchically constructed biological composite of polysaccharides, proteins and mineral, whose mechanical properties far surpass those of its component parts.
doi:10.1098/rsif.2006.0188
PMCID: PMC2373412  PMID: 17251136
biomineralization; nacre; molluscs; β-chitin
12.  Biologically inspired crack delocalization in a high strain-rate environment 
Biological materials possess unique and desirable energy-absorbing mechanisms and structural characteristics worthy of consideration by engineers. For example, high levels of energy dissipation at low strain rates via triggering of crack delocalization combined with interfacial hardening by platelet interlocking are observed in brittle materials such as nacre, the iridescent material in seashells. Such behaviours find no analogy in current engineering materials. The potential to mimic such toughening mechanisms on different length scales now exists, but the question concerning their suitability under dynamic loading conditions and whether these mechanisms retain their energy-absorbing potential is unclear. This paper investigates the kinematic behaviour of an ‘engineered’ nacre-like structure within a high strain-rate environment. A finite-element (FE) model was developed which incorporates the pertinent biological design features. A parametric study was carried out focusing on (i) the use of an overlapping discontinuous tile arrangement for crack delocalization and (ii) application of tile waviness (interfacial hardening) for improved post-damage behaviour. With respect to the material properties, the model allows the permutation and combination of a variety of different material datasets. The advantage of such a discontinuous material shows notable improvements in sustaining high strain-rate deformation relative to an equivalent continuous morphology. In the case of the continuous material, the shockwaves propagating through the material lead to localized failure while complex shockwave patterns are observed in the discontinuous flat tile arrangement, arising from platelet interlocking. The influence of the matrix properties on impact performance is investigated by varying the dominant material parameters. The results indicate a deceleration of the impactor velocity, thus delaying back face nodal displacement. A final series of FE models considered the identification of an optimized configuration as a function of tile waviness and matrix properties. In the combined model, the optimized configuration was capable of stopping the ballistic threat, thus indicating the potential for bioinspired toughened synthetic systems to defeat high strain-rate threats.
doi:10.1098/rsif.2011.0442
PMCID: PMC3284136  PMID: 21880614
nacre; dynamic impact; material discontinuity; interlocking; finite-element modelling
13.  Biotic Control of Skeletal Growth by Scleractinian Corals in Aragonite–Calcite Seas 
PLoS ONE  2014;9(3):e91021.
Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas.
doi:10.1371/journal.pone.0091021
PMCID: PMC3946587  PMID: 24609012
14.  Organization pattern of nacre in Pteriidae (Bivalvia: Mollusca) explained by crystal competition 
Bivalve nacre is a brick-wall-patterned biocomposite of aragonite platelets surrounded by organic matter. SEM–electron back scatter diffraction analysis of nacre of the bivalve family Pteriidae reveals that early aragonite crystals grow with their c-axes oriented perpendicular to the growth surface but have their a- and b-axes disoriented. With the accumulation of successive lamellae, crystals progressively orient themselves with their b-axes mutually parallel and towards the growth direction. We propose that progressive orientation is a result of competition between nacre crystals at the growth front of lamellae, which favours selection of crystals whose fastest growth axis (b-axis) is oriented parallel to the direction of propagation of the lamella. A theoretical model has been developed, which simulates competition of rhombic plates at the lamellar growth front as well as epitaxial growth of crystals onto those of the preceding lamella. The model predicts that disordered nacre progressively produces bivalve-like oriented nacre. As growth fronts become diffuse (as is the common case in bivalves) it takes longer for nacre to become organized. Formation of microdomains of nacre platelets with different orientations is also reproduced. In conclusion, not only the organic matrix component, but also the mineral phase plays an active role in organizing the final microstructure.
doi:10.1098/rspb.2005.3460
PMCID: PMC1560289  PMID: 16777720
biomineralization; microstructure; crystallography; shell; nacre; bivalves
15.  Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide 
Scientific Reports  2013;3:3164.
Nacre realizes strength and toughness through hierarchical designs with primary “brick and mortar” structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500 MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0–100%), and proposed an equation to depict the relationship.
doi:10.1038/srep03164
PMCID: PMC3819614  PMID: 24196491
16.  Biomineral Proteins from Mytilus edulis Mantle Tissue Transcriptome 
The common blue mussel, Mytilus edulis, has a bimineralic shell composed of approximately equal proportions of the two major polymorphs of calcium carbonate: calcite and aragonite. The exquisite biological control of polymorph production is the focus of research interest in terms of understanding the details of biomineralisation and the proteins involved in the process of complex shell formation. Recent advances in ease and availability of pyrosequencing and assembly have resulted in a sharp increase in transcriptome data for invertebrate biominerals. We have applied Roche 454 pyrosequencing technology to profile the transcriptome for the mantle tissue of the bivalve M. edulis. A comparison was made between the results of several assembly programs: Roche Newbler assembler versions 2.3, 2.5.2 and 2.6 and MIRA 3.2.1 and 3.4.0. The Newbler and MIRA assemblies were subsequently merged using the CAP3 assembler to give a higher consensus in alignments and a more accurate estimate of the true size of the M. edulis transcriptome. Comparison sequence searches show that the mantle transcripts for M. edulis encode putative proteins exhibiting sequence similarities with previously characterised shell proteins of other species of Mytilus, the Bivalvia Pinctada and haliotid gastropods. Importantly, this enhanced transcriptome has detected several transcripts that encode proteins with sequence similarity with previously described shell biomineral proteins including Shematrins and lysine-rich matrix proteins (KRMPs) not previously found in Mytilus.
Electronic supplementary material
The online version of this article (doi:10.1007/s10126-013-9516-1) contains supplementary material, which is available to authorized users.
doi:10.1007/s10126-013-9516-1
PMCID: PMC3896809  PMID: 23828607
Transcriptome; Bivalves; Biomineralisation; Mytilus
17.  A novel method for a multi-level hierarchical composite with brick-and-mortar structure 
Scientific Reports  2013;3:2322.
The fascination for hierarchically structured hard tissues such as enamel or nacre arises from their unique structure-properties-relationship. During the last decades this numerously motivated the synthesis of composites, mimicking the brick-and-mortar structure of nacre. However, there is still a lack in synthetic engineering materials displaying a true hierarchical structure. Here, we present a novel multi-step processing route for anisotropic 2-level hierarchical composites by combining different coating techniques on different length scales. It comprises polymer-encapsulated ceramic particles as building blocks for the first level, followed by spouted bed spray granulation for a second level, and finally directional hot pressing to anisotropically consolidate the composite. The microstructure achieved reveals a brick-and-mortar hierarchical structure with distinct, however not yet optimized mechanical properties on each level. It opens up a completely new processing route for the synthesis of multi-level hierarchically structured composites, giving prospects to multi-functional structure-properties relationships.
doi:10.1038/srep02322
PMCID: PMC3728589  PMID: 23900554
18.  Micromechanics of Sea Urchin Spines 
PLoS ONE  2012;7(9):e44140.
The endoskeletal structure of the Sea Urchin, Centrostephanus rodgersii, has numerous long spines whose known functions include locomotion, sensing, and protection against predators. These spines have a remarkable internal microstructure and are made of single-crystal calcite. A finite-element model of the spine’s unique porous structure, based on micro-computed tomography (microCT) and incorporating anisotropic material properties, was developed to study its response to mechanical loading. Simulations show that high stress concentrations occur at certain points in the spine’s architecture; brittle cracking would likely initiate in these regions. These analyses demonstrate that the organization of single-crystal calcite in the unique, intricate morphology of the sea urchin spine results in a strong, stiff and lightweight structure that enhances its strength despite the brittleness of its constituent material.
doi:10.1371/journal.pone.0044140
PMCID: PMC3439470  PMID: 22984468
19.  Hierarchical super-structure identified by polarized light microscopy, electron microscopy and nanoindentation: Implications for the limits of biological control over the growth mode of abalone sea shells 
BMC Biophysics  2012;5:19.
Background
Mollusc shells are commonly investigated using high-resolution imaging techniques based on cryo-fixation. Less detailed information is available regarding the light-optical properties. Sea shells of Haliotis pulcherina were embedded for polishing in defined orientations in order to investigate the interface between prismatic calcite and nacreous aragonite by standard materialographic methods. A polished thin section of the interface was prepared with a defined thickness of 60 μm for quantitative birefringence analysis using polarized light and LC-PolScope microscopy. Scanning electron microscopy images were obtained for comparison. In order to study structural-mechanical relationships, nanoindentation experiments were performed.
Results
Incident light microscopy revealed a super-structure in semi-transparent regions of the polished cross-section under a defined angle. This super-structure is not visible in transmitted birefringence analysis due to the blurred polarization of small nacre platelets and numerous organic interfaces. The relative orientation and homogeneity of calcite prisms was directly identified, some of them with their optical axes exactly normal to the imaging plane. Co-oriented "prism colonies" were identified by polarized light analyses. The nacreous super-structure was also visualized by secondary electron imaging under defined angles. The domains of the super-structure were interpreted to consist of crystallographically aligned platelet stacks. Nanoindentation experiments showed that mechanical properties changed with the same periodicity as the domain size.
Conclusions
In this study, we have demonstrated that insights into the growth mechanisms of nacre can be obtained by conventional light-optical methods. For example, we observed super-structures formed by co-oriented nacre platelets as previously identified using X-ray Photo-electron Emission Microscopy (X-PEEM) [Gilbert et al., Journal of the American Chemical Society 2008, 130:17519–17527]. Polarized optical microscopy revealed unprecedented super-structures in the calcitic shell part. This bears, in principle, the potential for in vivo studies, which might be useful for investigating the growth modes of nacre and other shell types.
doi:10.1186/2046-1682-5-19
PMCID: PMC3507795  PMID: 22967319
20.  An aminostratigraphy for the British Quaternary based on Bithynia opercula 
Quaternary Science Reviews  2013;61(C):111-134.
Aminostratigraphies of Quaternary non-marine deposits in Europe have been previously based on the racemization of a single amino acid in aragonitic shells from land and freshwater molluscs. The value of analysing multiple amino acids from the opercula of the freshwater gastropod Bithynia, which are composed of calcite, has been demonstrated. The protocol used for the isolation of intra-crystalline proteins from shells has been applied to these calcitic opercula, which have been shown to more closely approximate a closed system for indigenous protein residues. Original amino acids are even preserved in bithyniid opercula from the Eocene, showing persistence of indigenous organics for over 30 million years. Geochronological data from opercula are superior to those from shells in two respects: first, in showing less natural variability, and second, in the far better preservation of the intra-crystalline proteins, possibly resulting from the greater stability of calcite. These features allow greater temporal resolution and an extension of the dating range beyond the early Middle Pleistocene. Here we provide full details of the analyses for 480 samples from 100 horizons (75 sites), ranging from Late Pliocene to modern. These show that the dating technique is applicable to the entire Quaternary. Data are provided from all the stratotypes from British stages to have yielded opercula, which are shown to be clearly separable using this revised method. Further checks on the data are provided by reference to other type-sites for different stages (including some not formally defined). Additional tests are provided by sites with independent geochronology, or which can be associated with a terrace stratigraphy or biostratigraphy. This new aminostratigraphy for the non-marine Quaternary deposits of southern Britain provides a framework for understanding the regional geological and archaeological record. Comparison with reference to sites yielding independent geochronology, in combination with other lines of evidence, allows tentative correlation with the marine oxygen isotope record.
Highlights
► A stratigraphy using the intra-crystalline protein from the calcitic opercula of Bithynia is presented. ► Focused on Britain, but also using samples from a few continental sites, the coverage has been extended back to ∼3 Ma. ► This aminostratigraphy is consistent with independent geochronology, terrace stratigraphy and biostratigraphy. ► The aminostratigraphic framework has been linked to the marine oxygen isotope stratigraphy.
doi:10.1016/j.quascirev.2012.10.046
PMCID: PMC3566634  PMID: 23396683
Amino acid geochronology; Intra-crystalline protein decomposition; Palaeolithic; Pleistocene; Interglacial
21.  Water Soluble Bioactives of Nacre Mediate Antioxidant Activity and Osteoblast Differentiation 
PLoS ONE  2013;8(12):e84584.
The water soluble matrix of nacre is a proven osteoinductive material. In spite of the differences in the biomolecular compositions of nacre obtained from multiple species of oysters, the common biochemical properties of those principles substantiate their biological activity. However, the mechanism by which nacre stimulates bone differentiation remains largely unknown. Since the positive impact of antioxidants on bone metabolism is well acknowledged, in this study we investigated the antioxidant potential of a water soluble matrix (WSM) obtained from the nacre of the marine oyster Pinctada fucata, which could regulate its osteoblast differentiation activity. Enhanced levels of ALP activity observed in pre-osteoblast cells upon treatment with WSM, suggested the induction of bone differentiation events. Furthermore, bone nodule formation and up-regulation of bone differentiation marker transcripts, i.e. collagen type-1 and osteocalcin by WSM confirmed its ability to induce differentiation of the pre-osteoblasts into mature osteoblasts. Remarkably, same WSM fraction upon pre-treatment lowered the H2O2 and UV-B induced oxidative damages in keratinocytes, thus indicating the antioxidant potential of WSM. This was further confirmed from the in vitro scavenging of ABTS and DPPH free radicals and inhibition of lipid peroxidation by WSM. Together, these results indicate that WSM poses both antioxidant potential and osteoblast differentiation property. Thus, bioactivities associated with nacre holds potential in the development of therapeutics for bone regeneration and against oxidative stress induced damages in cells.
doi:10.1371/journal.pone.0084584
PMCID: PMC3868599  PMID: 24367677
22.  Participation of a cyanobacterial S layer in fine-grain mineral formation. 
Journal of Bacteriology  1992;174(24):7971-7981.
Cyanobacteria belonging to the Synechococcus group are ubiquitous inhabitants of diverse marine and freshwater environments. Through interactions with the soluble constituents of their aqueous habitats, they inevitably affect the chemistry of the waters they inhabit. Synechococcus strain GL24 was isolated from Fayetteville Green Lake, New York, where it has a demonstrated role in the formation of calcitic minerals. In order to understand the detailed interactions which lead to mineral formation by this organism, we have undertaken detailed ultrastructural studies of its cell surface and the initial events in mineral growth using a variety of electron microscopic and computer image enhancement techniques. Synechococcus strain GL24 has a hexagonally symmetrical S layer as its outermost cell surface component. The constituent protein(s) of this structure appears as a double band by sodium dodecyl sulfate-polyacrylamide gel electrophoresis with M(r)s of 104,000 and 109,000. We demonstrate that the S layer acts as a template for fine-grain gypsum and calcite formation by providing discrete, regularly arranged nucleation sites for the critical initial events in the mineralization process. To our knowledge, this is the first time that a bacterial S layer has been shown to have a role in mineral formation in a natural environment, and this report provides conclusive evidence for the specific involvement of bacterial surfaces in natural mineral formation processes.
Images
PMCID: PMC207533  PMID: 1459945
23.  Greenhouse conditions induce mineralogical changes and dolomite accumulation in coralline algae on tropical reefs 
Nature Communications  2014;5:3310.
Human-induced ocean acidification and warming alter seawater carbonate chemistry reducing the calcification of reef-building crustose coralline algae (CCA), which has implications for reef stability. However, due to the presence of multiple carbonate minerals with different solubilities in seawater, the algal mineralogical responses to changes in carbonate chemistry are poorly understood. Here we demonstrate a 200% increase in dolomite concentration in living CCA under greenhouse conditions of high pCO2 (1,225 μatm) and warming (30 °C). Aragonite, in contrast, increases with lower pCO2 (296 μatm) and low temperature (28 °C). Mineral changes in the surface pigmented skeleton are minor and dolomite and aragonite formation largely occurs in the white crust beneath. Dissolution of high-Mg-calcite and particularly the erosive activities of endolithic algae living inside skeletons play key roles in concentrating dolomite in greenhouse treatments. As oceans acidify and warm in the future, the relative abundance of dolomite in CCA will increase.
Ocean acidification is affecting the stability of coral reefs, but the exact mineralogical response is poorly understood. Diaz-Pulido et al. show that, under warming conditions, the relative abundance of dolomite increases by as much as 200% and could therefore slow the climate-induced break-up of coral reefs.
doi:10.1038/ncomms4310
PMCID: PMC3929803  PMID: 24518160
24.  Structure of first- and second-stage mineralized elements in teeth of the sea urchin Lytechinus variegatus 
Journal of structural biology  2009;168(3):452-466.
Microstructure of the teeth of the sea urchin Lytechinus variegatus was investigated using optical microscopy, SEM (scanning electron microscopy) and SIMS (secondary ion mass spectroscopy). The study focused on the internal structure of the first-stage mineral structures of high Mg calcite (primary, secondary and carinar process plates; prisms) and on morphology of the columns of second-stage mineral (very high Mg calcite) that cement the first-stage material together. Optical micrographs under polarized light revealed contrast in the centers (midlines) of carinar process plates and in prisms in polished sections; staining of primary and carinar process plates revealed significant dye uptake at the plate centers. Demineralization with and without fixation revealed that the midlines of primary and carinar process plates (but not secondary plates) and the centers of prisms differed from the rest of the plate or prism, and SIMS showed proteins concentrated in these plate centers. SEM was used to study the morphology of columns, the fracture surfaces of mature teeth and the 3D morphology of prisms. These observations of internal structures in plates and prisms offer new insight into the mineralization process and suggest an important role for protein inclusions within the first-stage mineral. Some of the 3D structures not reported previously, such as twisted prisms and stacks of carinar process plates with nested wrinkles, may represent structural strengthening strategies.
doi:10.1016/j.jsb.2009.07.013
PMCID: PMC2783381  PMID: 19616101
sea urchin; tooth; biomineralization; calcite; SIMS; SEM
25.  An improved failure criterion for biological and engineered staggered composites 
High-performance biological materials such as nacre, spider silk or bone have evolved a staggered microstructure consisting of stiff and strong elongated inclusions aligned with the direction of loading. This structure leads to useful combinations of stiffness, strength and toughness, and it is therefore increasingly mimicked in bio-inspired composites. The performance of staggered composites can be tuned; for example, their mechanical properties increase when the overlap between the inclusions is increased. However, larger overlaps may lead to excessive tensile stress and fracture of the inclusions themselves, a highly detrimental failure mode. Fracture of the inclusions has so far only been predicted using highly simplified models, which hinder our ability to properly design and optimize engineered staggered composites. In this work, we develop a new failure criterion that takes into account the complex stress field within the inclusions as well as initial defects. The model leads to an ‘optimum criterion’ for cases where the shear tractions on the inclusions is uniform, and a ‘conservative’ criterion for which the tractions are modelled as point forces at the ends of the overlap regions. The criterion can therefore be applied for a wide array of material behaviour at the interface, even if the details of the shear load transfer is not known. The new criterion is validated with experiments on staggered structures made of millimetre-thick alumina tablets, and by comparison with data on nacre. Formulated in a non-dimensional form, our new criterion can be applied on a wide variety of engineered staggered composites at any length scale. It also reveals new design guidelines, for example high aspect ratio inclusions with weak interfaces are preferable over inclusions with low aspect ratio and stronger interfaces. Together with existing models, this new criterion will lead to optimal designs that harness the full potential of bio-inspired staggered composites.
doi:10.1098/rsif.2012.0849
PMCID: PMC3565704  PMID: 23221990
nacre; biomimetic materials; fracture toughness; materials design; micromechanics; composite materials

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