Formation energies and site preference of substitutional divalent cations in carbonated apatite

First-principles calculations were performed to examine defect formation energies and site preference of substitutional divalent cations M²⁺ (M = Mg, Cu, Zn, Cd, Sr, Pb, and Ba) in hydroxyapatite (HAp, Ca₁₀(PO₄)₆(OH)₂) and carbonated apatite (CAp). All inequivalent substitutional sites of and M²⁺ were investigated to determine their most preferential sites. For all M²⁺ studied, their defect formation energies for the most stable substitutional sites were lower in CAp than in hydroxyapatite (HAp), demonstrating that M²⁺ are preferentially substituted into CAp over HAp. For Ca sites in CAp, correlations between the defect formation energies and Ca-O bond lengths showed that bigger and smaller M²⁺ than Ca²⁺ are preferentially substituted for Ca sites with longer and shorter bond lengths than those in HAp, respectively. In addition, Ca sites with lower coordination numbers than 6 are preferentially substituted by Zn²⁺ and Cu²⁺ that originally tend to form 4- or 5-fold coordination in their phosphate crystals. substitution is therefore likely to effectively stabilize substitutional foreign ions by modifying bond lengths and coordination numbers of Ca sites from those in pure HAp. These effects may play an important role in enhancing the M²⁺ solubility into CAp.     

Zinc as an essential trace element in the acceleration of matrix vesicles-mediated mineral deposition

BACKGROUND: Zinc (Zn) has a potent stimulatory effect on osteoblastic bone formation and an inhibitory effect on osteoclastic bone resorption. PURPOSE: The effect of Zn on the function of matrix vesicles (MVs) remains controversial. The purpose of this study was to investigate the effect of Zn on alkaline phosphatase (ALP) activity of osteoblasts and in the initial biological MVs‐mediated mineral deposition. STUDY DESIGN: Osteoblasts were treated with varying concentrations of Zn dissolved in culture medium. After three, five, and seven days of culture, ALP activity was assayed. For the detection of a low level of calcium concentration in MVs, X‐ray fluorescence (XRF) analyses were applied. The effect of Zn for the transformation of calcium phosphate was analyzed using a scanning electron microscope fitted with an energy dispersive X‐ray microanalysis (EDX) system. RESULTS: The ALP activity of osteoblasts in culture medium supplemented with 1 × 10^?5M of Zn was significantly increased at both five and seven days. XRF data demonstrated higher levels of calcium concentration over time in the Zn‐supplemented group. EDX data showed that mineral deposits beginning on day 3 were transformed from whitlockite to calcium phosphate near hydroxyapatite, and that Zn accelerated this transformation. CONCLUSIONS: The proper concentration of Zn increased the ALP activity of osteoblasts after five and seven days of incubation. The present XRF and EDX data suggest that the increase of mineral deposition with Zn exposure for one to five days might be mediated by the activation of ALP and calcium‐binding proteins. Microsc. Res. Tech., 2011. © 2011 Wiley Periodicals, Inc.     

Thermal conductivity analysis using three‐dimensional microstructures of gelation freezing derived cellular mullite

The relationship between thermal conductivity and unidirectional cellular mullite microstructures created with the freeze casting route is discussed using actual three‐dimensional (3D) images, in which a homogenization method was conducted with microscopic models created from 3D images, the temperature variation in macroscopic models by the finite element method (FEM), and local heat conduction in microscopic models. The simulation results were consistent with the experimental results. This image‐based modeling technique was thus confirmed to be a strong tool for the prediction of various thermal properties of porous ceramics.     

Characteristics of humic substances in the Kuji River waters as determined by high-performance size exclusion chromatography with fluorescence detection

Direct measurement by high-performance size exclusion chromatography with fluorescence detection was applied to the characterization of humic substances in river waters from the Kuji River system, which runs through forest hills and an agricultural plain in Japan. The monitoring wavelength of excitation 320 nm and emission 430 nm corresponds to the fluorescence maxima for aquatic fulvic acid. Chromatograms of the river waters showed four peaks; each peak position was in good agreement among these samples. Peak height ratios for the samples from the upstream Kuji River and its tributaries were different from those of the midstream and downstream sections of the Kuji River, which may reflect differences in the characteristics of humic substances and other organic materials supplied from soil to river.     

Long-chain polyamines (LCPAs) from marine sponge: possible implication in spicule formation

Two distinct marine organisms, diatoms and sponges, deposit dissolved silicates to construct highly architectural and species-specific body supports. Several factors such as proteins, long-chain polyamines (LCPAs), or polypeptides modified with LCPAs are known to be involved in this process. The LCPAs contained in the silica walls of diatoms are thought to play pivotal roles in the silica deposition. In sponges, however, a protein called silicatein and several other proteins have been reported to be the factors involved in the silica deposition. However, no other factors involved in this process have been reported. We have identified the LCPAs from the marine sponge Axinyssa aculeata and present here some evidence that sponge-derived LCPAs can deposit silica and that the LCPA derivatives are associated with spicules. The results indicate a common chemistry between sponges and diatoms, the two major players in the biological circulation of silicon in the marine environment. A wide variety of organisms are known to utilize silica in their biological processes. Polyamines or other functional molecules might be involved, in combination with proteins, in their biosilicification process.     

Toward an information-integrated control system—the control-theoretic view of intelligent control technology

Recent computing technology is providing alternative strategies for the functionality and implementation of controllers for practical complex systems. An important issue will be how to integrate all information about control problems. In this paper, we present the control-theoretic view of intelligent control technology, and discuss a paradigm for an information-integrated control system. This work was presented, in part, at the Third International Symposium on Artificial Life and Robotics, Oita, Japan, January 19–21, 1998     

Effect of thermal cycles on the mechanical strength of quad flat pack leads/Sn-3.5Ag-X (X=Bi and Cu) solder joints

Quad Flat Pack (QFP) Leads/Sn-3.5Ag-X (X=Bi and Cu) joint was thermally cycled between 243 K and 403 K or 273 K and 373 K, and both metallographic examination and mechanical pull test were performed to evaluate thermal fatigue damage of the joint. The addition of bismuth drastically degrades the thermal fatigue resistance of Sn-3.5Ag solder. On the other hand, the pull strength of Sn-3.5Ag-Cu solder joints slightly decreased with increasing number of thermal cycles, though it still remains higher in comparison to that for conventional Sn-37Pb or bismuth containing solder joint. The behavior observed here reflects the isothermal fatigue properties of bulk solder, because thermal fatigue crack initiates at the surface of solder fillet and propagates within the fillet in an early stage of fatigue damage. Furthermore, the lead phases lying at the interface between lead-frame and bismuth containing solder joint may promote the crack propagation at the interface, resulting in the extremely low thermal fatigue resistance of the joint.     

Numerical simulation of three-dimensional viscoelastic flow within dies

In recent years, the development of CAE (Computer Aided Engineering) in polymer processing has been remarkable, and it is expected to be more realistic in viscoelastic numerical simulation, particularly in three-dimensional complex geometry. Because of the problems of computational memory capacity, CPU time, and the numerical convergence of viscoelastic flow simulation, three-dimensional viscoelastic simulation applicable to industrial flow behaviors has not yet been attempted. In this paper, we developed the numerical simulation of three-dimensional viscoelastic flow within dies using a decoupled method, streamwise integration, and penalty function methods to decrease memory, and the TME (“Transformation of Equation of Motion to the Elliptic Equation,” S. Tanoue, T. Kajiwara, and K. Funatsu, The Eleventh Annual Meeting, the Polymer Processing Society Seoul, Korea, Extended Abstracts p.439) method, which raises the stability of convergence. We confirmed the reliability of this simulation technique to compare simulation results with experimental data of the stress field at a downstream wall shear rate of 5.41s^?1 within a 60° angle tapered contraction die. We compared the predictions of a viscoelastic model (Phan-Thien and Tanner model) with a pure viscosity model (Carreau model) at a downstream wall shear rate of 120s^?1 and discovered a remarkable effect of viscoelasticity in the shear stress and first normal stress difference in particular in the tapered region.     

Characterization of the ybdT gene product of Bacillus subtilis: Novel fatty acid β-hydroxylating cytochrome P450

We have characterized the gene encoding fatty acid α-hydroxylase, a cytochrome P450 (P450) enzyme, from Sphingomonas paucimobilis. A database homology search indicated that the deduced amino acid sequence of this gene product was 44% identical to that of the ybdT gene product that is a 48 kDa protein of unknown function from Bacillus subtilis. In this study, we cloned the ybdT gene and characterized this gene product using a recombinant enzyme to clarify function of the ybdT gene product. The carbon monoxide difference spectrum of the recombinant enzyme showed the characteristic one of P450. In the presence of H₂O₂, the recombinant ybdT gene product hydroxylated myristic acid to produce β-hydroxyristic acid and α-hydroxymyristic acid which were determined by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry. The amount of these products increased with increasing reaction period and amount of H₂O₂ in the reaction mixture. The amount of β-hydroxyl product was slightly higher than that of α-hydroxyl product at all times during the reaction. However, no reaction products were detected at any time or at any concentration of H₂O₂ when heat-inactivated enzyme was used. HPLC analysis with a chiral column showed that the β-hydroxyl product was nearly enantiomerically pure R-form. These results suggest that this P450 enzyme is involved in a novel biosynthesis of β-hydroxy fatty acid.     

Material performance of age-hardened beryllium–copper alloy,CDA-C17200, in a high-pressure,gaseous hydrogen environment

In order to develop safer and more energy-efficient, hydrogen pre-cooling systems for use in hydrogen refueling stations, it is necessary to identify a high-strength metallic material with greater thermal conductivity and lower susceptibility to hydrogen embrittlement, as compared with ordinary, stable austenitic stainless steels. To accomplish this task, the hydrogen compatibility of a precipitation-hardened, high-strength, copper-based alloy was investigated by slow-strain-rate tensile (SSRT), fatigue-life, fatigue-crack-growth (FCG) and fracture toughness tests in 115-MPa hydrogen gas at room temperature. The hydrogen solubility and diffusivity of the alloy were also determined. The hydrogen solubility of the alloy was two or three orders of magnitude lower than that of austenitic stainless steels. The alloy also demonstrated absolutely no hydrogen-induced degradation of its strength properties, a factor which could contribute to the reduction of costs related to the construction and maintenance of hydrogen refueling stations, owing to the downsizing and improved cooling performance of the pre-cooling systems.