Luminescence intensity in coral skeletons from Mona Island in the Caribbean Sea and its link to precipitation and wind speed

This study investigates the potential of using changes of interannual luminescence intensity in hermatypic Montastraea coral skeletons in the northeastern Caribbean as a proxy of precipitation and (trade) wind speed. In order to find wavelength pairs that are well suited to detect variations in the concentration of incorporated terrestrial humic substances in coral skeletons, and thus to reconstruct past run-off and rainfall, three-dimensional excitation-emission matrix fluorescence spectra of seawater samples were investigated on their relationships to local precipitation. Three prominent excitation-emission peaks at 310/430, 425/480 and 390/530 nm were identified. The fluorescence intensities of the wavelength pair 310/430 nm showed a weak relationship, while the wavelength pairs at 425/480 and 390/530 nm showed strong relationships with local precipitation. Variations in luminescence intensities from scans on the coral surface along the growth axis using the wavelengths identified were then compared with instrumental records of regional precipitation and wind speed. In the coral skeleton as well, the wavelength pairs at 425/480 and 390/530 nm were more strongly correlated with regional precipitation and wind speed. This indicates that these two wavelength pairs are well suited to reconstruct past precipitation and wind speed. In order to evaluate the use as a proxy of trade wind variability in the Caribbean, tropical Atlantic region, variations in luminescence intensity were compared with a record of trade wind variability from the southern Caribbean. The two records are strongly correlated, which suggests that luminescence intensity in coral skeletons, at least from Mona Island, can be used as proxy of trade wind variability and precipitation.     

Isotropic microscale mechanical properties of coral skeletons

Scleractinian corals are a major source of biogenic calcium carbonate, yet the relationship between their skeletal microstructure and mechanical properties has been scarcely studied. In this work, the skeletons of two coral species: solitary Balanophyllia europaea and colonial Stylophora pistillata, were investigated by nanoindentation. The hardness H_IT and Young''s modulus E_IT were determined from the analysis of several load–depth data on two perpendicular sections of the skeletons: longitudinal (parallel to the main growth axis) and transverse. Within the experimental and statistical uncertainty, the average values of the mechanical parameters are independent on the section''s orientation. The hydration state of the skeletons did not affect the mechanical properties. The measured values, E_IT in the 76–77 GPa range, and H_IT in the 4.9–5.1 GPa range, are close to the ones expected for polycrystalline pure aragonite. Notably, a small difference in H_IT is observed between the species. Different from corals, single-crystal aragonite and the nacreous layer of the seashell Atrina rigida exhibit clearly orientation-dependent mechanical properties. The homogeneous and isotropic mechanical behaviour of the coral skeletons at the microscale is correlated with the microstructure, observed by electron microscopy and atomic force microscopy, and with the X-ray diffraction patterns of the longitudinal and transverse sections.     

裂纹格特蛤韧带中的天然生物光子结构

采用光学显微镜、微型光纤光谱仪和扫描电镜对海产裂纹格特蛤韧带的光学性质以及纳米结构进行了研究。结果表明:韧带是由文石纤维和蛋白质组成的二维天然生物光子材料。另外,首次发现纤维的粒径和间距与韧带位置有关,其值从背侧的133 nm、149nm分别增大到腹侧的156nm、175nm,从而导致韧带反射谱自背侧至腹侧发生红移,反射峰分别位于476nm和544nm处。     

In-vitro study on calcium carbonate crystal growth mediated by organic matrix extracted from fresh water pearls

For the purpose of studying the mediation of organic matrix on the crystallization of calcium carbonate, water soluble matrix (WSM), acid soluble matrix (ASM) and acid insoluble matrix (AIM) were extracted from aragonite pearls and vaterite pearls respectively. Then, in-vitro calcium carbonate crystallization experiments under the control of these six organic matrices were carried out in the present study. Scanning electron microscopy (SEM) was utilized to observe the morphology of CaCO₃ and Raman spectroscopy as a powerful technique was used to distinguish the crystal polymorph. Influences of the six kinds of organic matrices on the calcium carbonate crystal growth are proposed. ASM of vaterite pearls can induce vaterite to crystallize and WSM of aragonite pearls mediates to produce aragonite crystals. The single AIM membranes of the two pearls have no pronounced effect on the CaCO₃ crystallization. Additionally, the crystal size obtained with the additive of WSM of the two kinds of pearls is smaller than that with the additive of ASM. Moreover, self-assembly phenomenon in the biomineralization process and the distorted morphology calcite are observed. Current results demonstrate important aspects of matrix protein-controlled crystallization, which is beneficial to the understanding of nacre biomineralization mechanism. Further study of the precise control of these matrix proteins on CaCO₃ crystal growth is being processed.     

Influence of the Molecular Structure and Morphology of Self-Assembled 1,3,5-Benzenetrisamide Nanofibers on their Mechanical Properties

The influence of molecular structure on the mechanical properties of self-assembled 1,3,5-benzenetrisamide nanofibers is investigated. Three compounds with different amide connectivity and different alkyl substituents are compared. All the trisamides form well-defined fibers and exhibit significant differences in diameters of up to one order of magnitude. Using nanomechanical bending experiments, the rigidity of the nanofibers shows a difference of up to three orders of magnitude. Calculation of Young's modulus reveals that these differences are a size effect and that the moduli of all systems are similar and in the lower GPa range. This demonstrates that variation of the molecular structure allows changing of the fibers' morphology, whereas it has a minor influence on their modulus. Consequently, the stiffness of the self-assembled nanofibers can be tuned over a wide range-a crucial property for applications as versatile nano- and micromechanical components.     

The spatial network of skeletal proteins in a stony coral

Coral skeletons are materials composed of inorganic aragonitic fibres and organic molecules including proteins, sugars and lipids that are highly organized to form a solid biomaterial upon which the animals live. The skeleton contains tens of proteins, all of which are encoded in the animal genome and secreted during the biomineralization process. While recent advances are revealing the functions and evolutionary history of some of these proteins, how they are spatially arranged in the skeleton is unknown. Using a combination of chemical cross-linking and high-resolution tandem mass spectrometry, we identify, for the first time, the spatial interactions of the proteins embedded within the skeleton of the stony coral Stylophora pistillata. Our subsequent network analysis revealed that several coral acid-rich proteins are invariably associated with carbonic anhydrase(s), alpha-collagen, cadherins and other calcium-binding proteins. These spatial arrangements clearly show that protein–protein interactions in coral skeletons are highly coordinated and are key to understanding the formation and persistence of coral skeletons through time.     

Thermally induced phase transformation of pearl powder

The polymorphic phase transformation of thermally treated pearl powder was investigated by X-ray diffraction and thermoanalytical techniques. The phase transformation was based on quantification of the calcite content at various temperatures using Rietveld refinement analysis. The results show that the phase transformation of pearl aragonite occurred within a temperature range of 360–410 °C, which is 50–100 °C lower than the range for non-biomineralized aragonite. These thermoanalytical results suggest that the phase transformation of pearl aragonite may occur immediately after the thermal decomposition of the organic matrix in the pearl powder. An important finding is that decomposition of the organic matrix may greatly facilitate such transformation by releasing additional space for an easier structural reconstruction during the phase transformation process.     

What is the difference in organic matrix of aragonite vs. vaterite polymorph in natural shell and pearl? Study of the pearl-forming freshwater bivalve mollusc Hyriopsis cumingii

Aragonite pearl, vaterite pearl and shell nacre of the freshwater mollusc Hyriopsis cumingii (Zhejiang province, China) were chosen to analyze microstructure and organic composition in the different habits of calcium carbonate. SEM and TEM were used to reveal the microstructure and mineralogical phase. We found that tablets in vaterite exhibited more irregular texture and were packaged with more organic matrices than in aragonite forms. Then a peculiar method was introduced to extract water soluble matrix (WSM), acid soluble matrix (ASM) and acid insoluble matrix (AIM) from the three samples, and biochemical analysis of these organic matrixes involved in crystal formation and polymorph selection was carried out. High performance liquid chromatography (HPLC) confirms the hydrophobic pattern of the organic matrix intermingled with mineral, the opposite of the early mobilizable water soluble fraction. Amino acid composition confirms hydrophobic residues as major components of all the extracts, but it reveals an imbalance in acidic residues rates in WSM vs. ASM and in aragonite vs. vaterite. Electrophoresis gives evidence for signatures in proteins with a 140 kDa material specific for aragonite in WSM. Conversely all ASM extracts reveal the presence of about 55 kDa components, including a discrete band in vaterite extract.     

Effects of thermal treatments on the structure of two black coral species chitinous exoskeleton

Black corals (Antipatharians) are colonial cnidarians whose branched tree-like skeleton is constituted of chitin fibrils inside a lipoproteic matrix. The arrangement of the constituents of these materials provides a structure with outstanding physical properties. In this study, the structural properties of black coral skeletons of Antipathes caribbeana and Antipathes pennacea species are explored by means of thermal treatments in the range from room temperature up to 400 °C and the subsequent analysis using X-ray diffraction (XRD), infrared spectroscopy (FTIR), and thermal analysis (DSC/TGA). The effects of thermal treatment from room temperature up to around 210 °C induce the enhancement of the bands in the FTIR spectra and X-ray diffractograms, above that temperature, the FTIR and X-ray peaks become strongly attenuated. These effects are specially observed in the infrared bands associated to chitin at 3298 cm⁻¹ and to the secondary amide stretching around 1663 cm⁻¹, in particular, allowing the identification of the α-chitin in the black coral. XRD shows that the crystallinity index of the black coral chitin at room temperature is 24% and grows when the temperature increases, reaching a maximum value of 37% at 210 °C and decreases for higher temperatures. In addition, DSC and TGA measurements allowed identifying the most important transformation stages during the thermal treatments, namely, evaporation of water and the beginning and progress of degradation, depolymerization, and denaturation processes and finally, the degradation of the main functional groups of coral skeleton and coral chitin, in which the polysaccharide structure of chitin is depolymerized and the protein matrix is denatured.     

Flexural properties of glass fiber reinforced composite with multiphase biopolymer matrix

The aim of this study was to evaluate flexural properties of glass fiber-reinforced composites with a multiphase biopolymer matrix. Continuous unidirectional E-glass fibers were preimpregnated with a novel biopolymer of poly(hydroxyproline) amide and ester. The preimpregnated fibers were then further impregnated in a co-monomer system of Bis-GMA-TEGDMA, which formed semi-interpenetrating polymer networks (semi-IPN) with the preimpregnated polymer. After light initiated polymerization of the monomer system, rectangular shaped bar specimens (n = 4) were tested by the three-point bending test. The control material was a fiber-reinforced composite with a Bis-GMA-TEDGMA-matrix only. The mean flexural strength of poly(hydroxyproline) amide preimpregnated fiber composite was higher than that of the control (FS = 888 vs. 805 MPa). The poly(hydroxyproline) ester preimpregnated fibers resulted in lower strength (FS = 541 MPa). The results of this study suggest that preimpregnation of glass fibers with poly(hydroxyproline) amide and the use of such fibers in fiber-reinforced composites with IPN polymer matrices, can reach relatively high mechanical properties.     

水灰比对PVA纤维增强水泥基复合材料性能和显微结构的影响

对3种不同水灰比(0.2,0.4,0.65)形成的聚乙烯醇(PVA)纤维增强水泥基材料,通过三点弯曲试验,结合表观裂缝形状和裂缝处PVA纤维形态,研究了水灰比对材料弯曲性能的影响;通过对断裂面处纤维表面、纤维嵌入端和纤维拉断或拔出端的SEM影像分析,从微观层面研究了水灰比对PVA纤维-基体界面显微结构的影响。弯曲试验结果表明:随着水灰比增加,跨中部位裂缝数量明显增加,裂缝处拔出的纤维数量增多而拉断的数量减少,材料的弯曲韧度和开裂强度到弯曲强度的增强幅度提高。界面显微结构表明:随着水灰比增加,基体结构由致密变疏松,界面粘结力减弱,桥接裂缝的PVA纤维状态由瞬间猝断转变为滑动拔出且表面有轻微刮削,纤维对材料增强增韧的效率显著提高。     

Microstructure of aragonite grown at an air–liquid interface

Aragonite particles dispersed in a bioresorbable polymer matrix are considered to be a good candidate for bone prosthesis materials. It is important to characterize the microstructure of synthetic aragonite used for biomedical applications, since the microstructure may influence its integration, resorption and replacement by bone. We studied late stages of aragonite growth, at an air–liquid interface, from a solution not doped with additives. Comparison was made between the types of synthetic aragonite microstructure and that of aragonite which is found in nature (mollusc shells, gallstones, Earth's crust). The microstructure of natural aragonite is unique to certain classes of living organisms and the understanding of its structure/function relationships may help to select the types of synthetic aragonite for specific biomedical applications. Three types of synthetic aragonite were observed based on grain size and grain morphology. This revised version was published online in November 2006 with corrections to the Cover Date.     

Resistance of fibrous reinforced silver matrix composites to repeated make-break arc erosion

The resistance of fibrous reinforced silver matrix composites to repeated make-break arc erosion has been investigated in this study. Three different types of short fibers were used as reinforcements, including graphite short fibers, Saffil short fibers, and silicon carbide whiskers. The weight losses of eroded composites increase with fiber content, applied current, and test number due to the worse thermal conductivity of the composites and the higher remained temperatures on contact surfaces. The composites reinforced with Saffil short fibers exhibit the best erosion resistance of all reinforcements in the study because of the small spacings between Saffil short fibers and the strengthening of strong short-fiber skeletons. The effective contribution of short fibers to arc erosion resistance depends on their sizes to construct small-spacing and deeply-embedded skeletons.     

不同生长期贝壳的结构和力学性能

研究了腹足纲香螺贝壳在生长过程中不同时期的壳体材料结构及力学性能。结果表明, 随着贝壳的长大, 贝壳文石板片厚度增大, 各项力学性能指标也随之提高。贝壳体在生长过程中通过软体组织修改所产生的结构和贝壳的性能也在随之而演变。贝壳类天然生物材料的性能不同于传统工程材料中组织特征尺寸越小强度越高的准则, 需要考虑贝壳材料本身的微观结构、 组成和界面等多方面因素。      

Toughening mechanisms in bioinspired multilayered materials

Outstanding mechanical properties of biological multilayered materials are strongly influenced by nanoscale features in their structure. In this study, mechanical behaviour and toughening mechanisms of abalone nacre-inspired multilayered materials are explored. In nacre''s structure, the organic matrix, pillars and the roughness of the aragonite platelets play important roles in its overall mechanical performance. A micromechanical model for multilayered biological materials is proposed to simulate their mechanical deformation and toughening mechanisms. The fundamental hypothesis of the model is the inclusion of nanoscale pillars with near theoretical strength (σ_th ~ E/30). It is also assumed that pillars and asperities confine the organic matrix to the proximity of the platelets, and, hence, increase their stiffness, since it has been previously shown that the organic matrix behaves more stiffly in the proximity of mineral platelets. The modelling results are in excellent agreement with the available experimental data for abalone nacre. The results demonstrate that the aragonite platelets, pillars and organic matrix synergistically affect the stiffness of nacre, and the pillars significantly contribute to the mechanical performance of nacre. It is also shown that the roughness induced interactions between the organic matrix and aragonite platelet, represented in the model by asperity elements, play a key role in strength and toughness of abalone nacre. The highly nonlinear behaviour of the proposed multilayered material is the result of distributed deformation in the nacre-like structure due to the existence of nano-asperities and nanopillars with near theoretical strength. Finally, tensile toughness is studied as a function of the components in the microstructure of nacre.     

炭纤维生物膜的形成机制——I、炭纤维表面特性对微生物固着化的影响

采用对比方法，借助化学分析、表面形态分析及生物相容性表征技术等系统地研究了以活性炭纤维、表面改性活性炭纤维作为细胞固着化载体的表面特性及对微物固着的影响。重点考察了纤维表面官能团、比表面积、润湿性等表面特性对微生物固着化的影响。研究结果表明：（1）炭纤维表面的吸附特性对微生物的初期固着起着重要的作用，具有高比表面积的活性炭纤维更易于微生物固着并挂膜。（2）炭纤维表面润湿性与某些酸性官能团的适量增加，有益于载体表面微生物的固着。（3）炭纤维尤其是活性炭纤维较市售有机高分子材料具有更加优异的生物相容性，前者的微生物固着化速率是后者的4倍－16倍。     

Formation of novel morphologies of aragonite induced by inorganic template

A glass-slice was used as a template to induce formation and assembly of aragonite. Thermodynamic theory was applied to explain the production of the aragonite. Transformation of three-dimensional nucleation to template-based two-dimensional surface nucleation caused the production of aragonite. Hemisphere, twinborn hemisphere and flower-shaped particles were produced by direction of the glass-slices. Planes were always appeared in these as-synthesized samples because the nucleation and the growth of these samples were adsorbed at the surfaces of the glass-slices. The formation mechanism of the as-formed sample was proposed. Compared with organic template, the present study provides a facile method to apply inorganic template to prepare functional materials.     

Comparative study on nano-mechanics and thermodynamics of fish otoliths

Fish otolith is a kind of typical natural biomineral, which is composed of calcium carbonate and organic matrix. In fresh water carp otolith, the inorganic phase of lapillus is pure aragonite, and for asteriscus it is pure vaterite. In this research, the phase composition, phase transformation, mechanical property and solubility of lapillus and asteriscus were studied. And results showed that, the organic content of lapillus was higher than that of asteriscus; the phase-transition temperature of lapillus (aragonite–calcite) and asteriscus (vaterite–calcite) both happened between 520 and 640 °C; the nano-mechanical property of lapillus was better than that of asteriscus; the solubility of asteriscus powder was higher than that of lapillus powder.     

Growth and structure in abalone shell

The growth and self-assembly of aragonitic calcium carbonate found in the shell of abalone (Haliotis) is described. This was accomplished through the close examination of laboratory-grown flat pearl samples and cross-sectional slices of the nacreous shell. Further understanding of the sequenced assembly has been obtained. It has been confirmed that the growth of the aragonite component of the composite occurs by the successive nucleation of aragonite crystals and their arrest by means of a protein-mediated mechanism; it takes place in the “Christmas-tree pattern” [Nature 49 (1994) 371]. It is shown that the protein layer is virtually absent where plates on a same plane abut (along lateral surfaces of tiles). This suggests a mechanism of c-axis aragonite growth arrest by the deposition of a protein layer of approximately 20–30 nm that is periodically activated and determines the thickness of the aragonite platelets, which are remarkably constant (0.5 μm). This platelet size was measured for animals with shell diameters of 10, 50, and 200 mm and was found to be constant. The overall growth process is expressed in terms of parameters incorporating the anisotropy of growth velocity in aragonite (V_c, the velocity along c axis, and V_ab, the velocity in basal plane). Comparison of laboratory-raised and naturally-grown abalone indicates growth regulated by the level of proteinaceous saturation. Naturally-grown abalone exhibits mesolayers (growth bands) 0.3 mm apart; it is proposed that they result from seasonal interruptions in feeding patterns, creating thicker (10–20 μm) layers of protein. These mesolayers play a critical role in the mechanical properties, and are powerful crack deflectors. The viscoplastic deformation of the organic inter-tile layers is responsible for the significant improvement of tensile strength over the tensile strength of monolithic aragonite.     

Structure-property relations for silicon nitride matrix composites reinforced with pyrolytic carbon pre-coated Hi-Nicalon fibers

Si₃N₄ matrix composites reinforced with pyrolytic carbon pre-coated Hi-Nicalon (SiC) fibers, were studied using tensile testing and transmission electron microscopy. Three types of samples were evaluated all with a nominal coating thickness of 200 nm. The composites were densified by hot pressing at 1550 °C (type I and II) and at 1600 °C (type III). The fibers were coated with pyrolytic carbon via CVD with identical (sample I) and opposite (samples II and III) directions of the gas flow and of the fiber movement through the reactor. Tensile testing indicated for the three sample types respectively: brittle behaviour with huge pull out of the fibers, pseudo-plastic behaviour and brittle behaviour with little pull out. TEM indicated for the three sample types debonding typically at the fiber/coating interface, at the coating/matrix interface and in the coating, respectively. The relation between processing, structure, particularly of the coating and its interfaces with the matrix and the fibers and mechanical properties is addressed.