Diversified Biomineralization Roles of Pteria penguin Pearl Shell Lectins as Matrix Proteins.

Previously, we isolated jacalin-related lectins termed PPL2, PPL3 (PPL3A, 3B and 3C) and PPL4 from the mantle secretory fluid of Pteria penguin (Mabe) pearl shell. They showed the sequence homology with the plant lectin family, jacalin-related ß-prism fold lectins (JRLs). While PPL3s and PPL4 shared only 35%-50% homology to PPL2A, respectively, they exhibited unique carbohydrate binding properties based on the multiple glycan-binding profiling data sets from frontal affinity chromatography analysis. In this paper, we investigated biomineralization properties of these lectins and compared their biomineral functions. It was found that these lectins showed different effects on CaCO3 crystalization, respectively, although PPL3 and PPL2A showed similar carbohydrate binding specificities. PPL3 suppressed the crystal growth of CaCO3 calcite, while PPL2A increased the number of contact polycrystalline calcite composed of more than one crystal with various orientations. Furthermore, PPL4 alone showed no effect on CaCO3 crystalization; however, PPL4 regulated the size of crystals collaborated with N-acetyl-D-glucosamine and chitin oligomer, which are specific in recognizing carbohydrates for PPL4. These observations highlight the unique functions and molecular evolution of this lectin family involved in the mollusk shell formation.

Glycan Binding Profiling of Jacalin-Related Lectins from the Pteria Penguin Pearl Shell.

We determined the primary structures of jacalin-related lectins termed PPL3s (PPL3A, 3B, and 3C, which are dimers consisting of sequence variants α + α, α + ß, ß + ß, respectively) and PPL4, which is heterodimer consisting of α + ß subunits, isolated from mantle secretory fluid of Pteria penguin (Mabe) pearl shell. Their carbohydrate-binding properties were analyzed, in addition to that of PPL2A, which was previously reported as a matrix protein. PPL3s and PPL4 shared only 35-50% homology to PPL2A, respectively; they exhibited significantly different carbohydrate-binding specificities based on the multiple glycan binding profiling data sets from frontal affinity chromatography analysis. The carbohydrate-binding specificity of PPL3s was similar to that of PPL2A, except only for Man3Fuc1Xyl1GlcNAc2 oligosaccharide, while PPL4 showed different carbohydrate-binding specificity compared with PPL2A and PPL3s. PPL2A and PPL3s mainly recognize agalactosylated- and galactosylated-type glycans. On the other hand, PPL4 binds to high-mannose-and hybrid-type N-linked glycans but not agalactosylated- and galactosylated-type glycans.

Off-stoichiometry and molybdenum substitution effects on elastic moduli of B1-type titanium carbide.

B1-type MX ceramics are composed of transition metals (M) and C, N, and/or O (X) occupying the M and X sites, respectively, and having M-X nearest neighbor (NN) bonds and M-M and X-X next nearest neighbor (NNN) bonds. Substitution of the elements and the formation of structural vacancies in B1-type ceramics change the numbers and strengths of the bonds, leading to novel properties. The change in elastic modulus of off-stoichiometric TiC in equilibrium with a Ti-Mo solid solution phase was experimentally investigated based on the rule of mixtures from the Voigt model. The experimentally obtained values agreed well with the results of density functional theory calculations. The bulk modulus (K) of TiC increased from 205.6 to 239.2 GPa as the fraction of Ti sites occupied by Mo increased from 0.11 to 0.33, whereas the Young's modulus (E) and the shear modulus (G) remained nearly constant. On the other hand, all three elastic moduli decreased with increasing vacancy fraction at the C sites. These results suggest that the M-X bond strength should be the dominant factor in these moduli and the effect of M-M bond on K is greater than that of G and E.

Study of solidification pathway of a MoSiBTiC alloy by optical thermal analysis and in-situ observation with electromagnetic levitation.

MoSiBTiC alloys are promising candidates for next-generation ultrahigh-temperature materials. However, the phase diagram of these alloys has been unknown. We have developed an ultrahigh-temperature thermal analyser based on blackbody radiation that can be used to analyse the melting and solidification of the alloy 67.5Mo-5Si-10B-8.75Ti-8.75 C (mol%). Furthermore, electromagnetic levitation (EML) was used for in-situ observation of solidification and microstructural study of the alloy. On the basis of the results, the following solidification pathway is proposed: Mo solid solution (Moss) begins to crystallize out as a primary phase at 1955 °C (2228 K) from a liquid state, which is followed by a (Moss+TiC) eutectic reaction starting at 1900 °C (2173 K). Molybdenum boride (Mo2B) phase precipitates from the liquid after the eutectic reaction; however, the Mo2B phase may react with the remaining liquid to form Moss and Mo5SiB2 (T2) as solidification proceeds. In addition, T2 also precipitates as a single phase from the liquid. The remaining liquid reaches the (Moss + T2 + TiC) ternary eutectic point at 1880 °C (2153 K), and the (Moss + T2 + Mo2C) eutectic reaction finally occurs at 1720 °C (1993 K). This completes the solidification of the MoSiBTiC alloy.

Ultrahigh-temperature tensile creep of TiC-reinforced Mo-Si-B-based alloy.

In this study, the ultrahigh-temperature tensile creep behaviour of a TiC-reinforced Mo-Si-B-based alloy was investigated in the temperature range of 1400-1600 °C at constant true stress. The tests were performed in a stress range of 100-300 MPa for 400 h under vacuum, and creep rupture data were rationalized with Larson-Miller and Monkman-Grant plots. Interestingly, the MoSiBTiC alloy displayed excellent creep strength with relatively reasonable creep parameters in the ultrahigh-temperature range: a rupture time of ~400 h at 1400 °C under 137 MPa with a stress exponent (n) of 3 and an apparent activation energy of creep (Qapp) of 550 kJ/mol. The increasing rupture strains with decreasing stresses (up to 70%) and moderate strain-rate oscillations in the creep curves suggest that two mechanisms contribute to the creep: phase boundary sliding between the hard T2 and (Ti,Mo)C phases and the Moss phase, and dynamic recovery and recrystallization in Moss, observed with orientation imaging scanning electron microscopy. The results presented here represent the first full analysis of creep for the MoSiBTiC alloy in an ultrahigh-temperature range. They indicate that the high-temperature mechanical properties of this material under vacuum are promising.

Novel matrix proteins of Pteria penguin pearl oyster shell nacre homologous to the jacalin-related ß-prism fold lectins.

Nacreous layers of pearl oyster are one of the major functional biominerals. By participating in organic compound-crystal interactions, they assemble into consecutive mineral lamellae-like photonic crystals. Their biomineralization mechanisms are controlled by macromolecules; however, they are largely unknown. Here, we report two novel lectins termed PPL2A and PPL2B, which were isolated from the mantle and the secreted fluid of Pteria penguin oyster. PPL2A is a hetero-dimer composed of α and γ subunits, and PPL2B is a homo-dimer of ß subunit, all of which surprisingly shared sequence homology with the jacalin-related plant lectin. On the basis of knockdown experiments at the larval stage, the identification of PPLs in the shell matrix, and in vitro CaCO3 crystallization analysis, we conclude that two novel jacalin-related lectins participate in the biomineralization of P. penguin nacre as matrix proteins. Furthermore, it was found that trehalose, which is specific recognizing carbohydrates for PPL2A and is abundant in the secreted fluid of P. penguin mantle, functions as a regulatory factor for biomineralization via PPL2A. These observations highlight the unique functions, diversity and molecular evolution of this lectin family involved in the mollusk shell formation.