Hydrolysis of tetracalcium phosphate in H3PO4 and KH2PO4

The activity product of tetracalcium phosphate (TTCP, Ca₄(PO₄)₂O), was determined at 37°C, and the hydrolysis of TTCP was investigated in 0.01–0.1 mol l^–1 H₃PO₄ and KH₂PO₄ solutions by means of calcium and phosphorus analyses, X-ray diffraction and infrared analysis. The activity product, defined as K _sp=(Ca²⁺)⁴ (PO ₄ ^3– )² (OH^–)², was 37.36 as pK _sp, which was smaller than that previously reported (42.4). TTCP easily hydrolysed to form calcium-deficient apatite (Ca-def OHAp, Ca_5–x (HPO₄) _x (PO₄)_3–x (OH)_1–x ), or dicalcium phosphate dihydrate (DCPD, CaHPO₄2H₂O), depending on the initial phosphate concentration. With 0.1 mol l^–1 H₃PO₄, TTCP hydrolysed to form DCPD within several minutes. In 0.025 mol l^–1 H₃PO₄ and 0.1 mol l^–1 KH₂PO₄, TTCP hydrolysed to form Ca-def OHAp through DCPD. In the latter solution, a small amount of octacalcium phosphate (OCP, Ca₈(H₂PO₄)₂(PO₄)₄5H₂O), was detected as an intermediate product. In 0.025 mol l^–1 KH₂PO₄, TTCP hydrolysed directly to form Ca-def OHAp. In 0.01 mol l^–1 H₃PO₄, hydrolysis of TTCP was not completed, although Ca-def OHAp was only a product. Thus the final product and the degree of hydrolysis depended on the pH and the overall Ca/P ratio in the reaction system. The rate of Ca-def OHAp formation seemed to be controlled by the dissolution rate of TTCP rather than the crystallization rate of the OHAp.     

Corrosion evaluation of Au-Cu-Pd ternary alloys

The corrosion resistivity of single-phase Au-Cu-11 at% Pd alloys was evaluated by using a parameterQ which represented the total amount of anodic reaction in a potentiostatic polarization test. The result was compared with those for binary Au-Cu, ternary Au-Cu-11 at % Ag and some commercial alloys. The validity of usingQ as a corrosion parameter was confirmed by the good agreement between the analysed and calculated values of copper ion dissolved into the test solution. By replacing a part of the copper in Au-Cu alloys with palladium the corrosion resistivity can be greatly improved, but silver has no such significant effect. The value ofQ decreased by both treatments of homogenization and grain refinement of the alloy. One of the advantages of the alloy having a single-phase structure is that inhomogeneity in the distribution of the constituents is small even in the as-cast state, which results in a small galvanic effect.     

Ion-spray mass spectrometry for identification of the nonreducing terminal sugar of glycosaminoglycan

Various oligosaccharides from hyaluronic acid, which have glucuronic acid or N- acetylglucosamine at the nonreducing terminal, were prepared by digestion with a combination of testicular hyaluronidase and beta-glucuronidase. These oligo saccharides were analyzed by negative-mode ion-spray mass spectrometry (MS) with an atmospheric pressure ion source. Introduction of collisionally activated dissociation tandem mass spectrometry (CAD-MS/MS) produced ions derived from cleavage of the glycosidic bonds, allowing the structure to be analyzed. The CAD-MS/MS spectrum showed an intense and characteristic fragment ion at m/z 193 for oligosaccharides having glucuronic acid at the nonreducing terminal. On the other hand, this ion was not observed in the spectra of oligosaccharides having N- acetylglucosamine at the nonreducing terminal. Therefore, the fragmentation pattern revealed by CAD-MS/MS provides useful information for distinguishing glucuronic acid and N- acetylglucosamine at the nonreducing terminal of oligosaccharides derived from hyaluronic acid and other glycosaminoglycans. This ion-spray CAD-MS/MS technique was also applied successfully to the characterization of glycosaminoglycans reconstructed by glycotechnology.     

Computer simulations of anodic dissolution in Cu-Au-Pd ternary alloys

Computer simulation experiments were performed for the anodic dissolution process of Cu_0.7Au_0.3–x Pd _x (x=0–0.3) alloys. Dissolution probabilities of constituents which represented the dissolution rate were defined by considering the standard electrode potential of the dissolution reaction and atomic interaction between Cu and the other atoms. The simulation results qualitatively reproduced the experimental results of anodic potentiostatic polarization tests regarding the dependence of the anodic dissolution behaviour on the polarization potential and the alloy composition, and the atomic concentration depth profile of the constituents after anodic polarization. Atomic interaction among the constituents of an alloy was found to be one of the important factors which control the anodic dissolution features of the alloys.     

Development of lateral displacement sensor for real‐time detection of structural damage

We have developed a novel sensor that enables us to measure the relative story displacement of a building structure in real time. This lateral displacement sensor (LDS) is composed of a light‐emitting diode (LED) array, which is fixed on the ceiling, and a position‐sensitive detector (PSD) unit, which is placed on the floor. We optimized the LDS to achieve high accuracy in lateral displacement measurement. The accuracy was evaluated to be 60 µm by conducting shaking table tests. Two LDSs were implemented in an actual building equipped with an active variable stiffness (AVS) system, and the building was vibrated with seismic waveforms by an exciter placed on the rooftop. The seismic displacement of the second floor relative to the first floor was measured using the LDS. Furthermore, the inclination angle of the second floor could be measured using the LDS during the seismic vibration. Using the AVS system, we realized the residual displacement of the second floor without inducing damage to the building, and succeeded in real‐time residual displacement measurement for the first time. These results indicate that the LDS is useful for the health diagnosis of a building structure. © 2011 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Effect of molding pressure on fabrication of low-crystalline calcite block

We have reported that low-crystalline porous calcite block, which is useful as a bone substitute or a source material to prepare apatite-type bone fillers could be fabricated by exposing calcium hydroxide compact to carbon dioxide gas saturated with water vapor. In the present study, we investigated the effect of molding pressure on the transformation of calcium hydroxide into calcite and the mechanical strength of the carbonated compact. Transformation into calcite was almost completed within 72 h, however, a small amount of Ca(OH)₂ still remained unreacted at higher molding pressure because of incomplete penetration of CO₂ gas into the interparticle space due to dense packing of Ca(OH)₂ particles. On the other hand, high molding pressure resulted in an increase in diametral tensile strength (DTS) of the calcite compact formed. Critical porosity of the calcite block was calculated as approximately 68%.     

A 1-V high-speed MTCMOS circuit scheme for power-down applicationcircuits

This paper proposes a new multithreshold-voltage CMOS circuit (MTCMOS) concept aimed at achieving high-speed, ultralow-power large-scale integrators (LSI's) for battery-driven portable equipment. The “balloon” circuit scheme based on this concept preserves data during the power-down period in which the power supply to the circuit is cut off in order to reduce the standby power. Low-power, high-speed performance is achieved by the small preserving circuit which can be separated from the critical path of the logic circuit. This preserving circuit is not only three times faster than a conventional MTCMOS one, but it consumes half the power and takes up half the area. Using this scheme for an LSI chip, 20-MHz operation at 1.0 V and only a few nA standby current was achieved with 0.5-μm CMOS technology. Moreover, this scheme is effective for high speed and low-power operation in quarter-micrometer and finer devices     

A core-shell-type fluorescent nanosphere possessing reactive poly(ethylene glycol) tethered chains on the surface for zeptomole detection of protein in time-resolved fluorometric immunoassay

To increase the sensitivity and to depress the nonspecific binding in biochemical assays, a new core-shell-type fluorescent nanosphere (106.7 nm) covalently conjugated with antibody was prepared. The core-shell-type nanosphere was constructed by dispersion radical polymerization of styrene in the presence of heterotelechelic poly(ethylene glycol) (PEG) macromonomer, which has a polymerizable vinylbenzyl group at one end and a primary amino group at the other chain end and used as well as a surfactant. The resulting nanosphere had PEG tethered chains on the surface, which possesses a primary amino group at the distal end of the PEG chain (NH(2) nanosphere). The fluorescent NH(2) nanosphere was constructed by incorporating fluorescent europium chelates with beta-diketonate ligands in the core of the NH(2) nanosphere by means of a physical entrapment method. The primary amino groups on the fluorescent NH(2) nanosphere were then converted to maleimide groups using a hetero cross-linker. The resulting nanosphere had maleimide groups on the surface (maleimide nanosphere), onto which proteins having SH group in the molecule could be covalently conjugated quantitatively without any denaturation of the proteins under the milder reaction condition. The applicability of the fluorescent nanosphere was tested in a model sandwich immunoassay for alpha-fetoprotein (AFP) determination. Anti-human AFP Fab' fragment was covalently conjugated onto the maleimide nanosphere (Fab' nanosphere), and it was used for the solid-phase time-resolved fluorometric immunoassay of AFP. The detection limit (mean + 2 SD) was 0.040 pg/mL or 57.1 zmol (57.1 x 10(-)(21) mol, M(w,AFP) = 70000) for AFP. The imprecision (concentration CV) over the whole assay range was 1.1% (100 pg/mL) - 17.1% (0.1 pg/mL), even though with this conjugation of antibody to the nanosphere, the nonspecific binding was practically negligible (0.0008%) and even when approximately 1.9 x 10(9) particles of the Fab' nanosphere were applied to the microtitration well.     

Effect of mixing ratio and pH on the reaction between Ca4(PO4)2O and CaHPO4

The reaction of _Ca(PO₄)₂O (TTCP) and CaHPO₄ (DCPA) in an aqueous solution has been shown to be responsible for the hardening of a calcium phosphate cement. This reaction was investigated by monitoring pH changes and composition of solid phases. In the first set of experiments (no attempt to control pH), 2.5 g each of mixtures of TTCP/DCPA, molar ratio from 0.25 to 2, was placed in 12.5 mL of 0.15 mol/L KCl solution, at initial pH about 7, and the pH was allowed to drift for 24 h. Results show that at any time up to 24 h, the pHs were higher for slurries with higher TTCP/DCPA molar ratios. For the slurries with TTCP/DCPA molar ratio of 0.83, the 24 h pHs of the slurries were 9 to 11, whereas for those with TTCP/DCPA of 0.67, the pHs were between 5.3 and 7. The slurries with TTCP/DCPA molar ratios between 0.5 and 1 (Ca/P molar ratio=1.5 to 1.67) reacted completely within 24 h to form hydroxyapatite(OHAp), Ca₅(PO₄)₃OH. In the second set of experiments, 2 g of an equimolar TTCP and DCPA mixture was placed in 20 mL of 0.15 mol/L KCl solution. The pH values were kept constant (6, 8 or 10) by using H₃PO₄ and Ca(OH)₂ or HCl and KOH as titrant solutions. At pH 8, DCPA and TTCP dissolved at about the same rate, whereas at pH 10, DCPA was consumed more rapidly than TTCP. At both pHs, OHAp was the only product formed. However, at pH 6, the composition of reaction products depended on the types of the titrants used. Specifically when H₃PO₄ and _Ca(OH)₂ were used, hydrolysis of TTCP was the predominant reaction and both octacalcium phosphate and OHAp were formed. But, when HCl and KOH were used, only OHAp was formed. In this case hydrolysis of TTCP and DCPA appeared to proceed independently with TTCP hydrolysis beginning immediately and progressing slowly through 48 h while the DCPA hydrolysis began several hours after the reaction started but was completed in 24 h. ©2000 Kluwer Academic Publishers