Hydrothermal modification of natural zeolites to improve uptake of ammonium ions

The modification of natural zeolites was carried out under hydrothermal conditions to improve the effectiveness of the uptake of ammonium ions. Natural zeolites originating in Japan, such as mordenite and clinoptilolite with quartz, feldspar and a trace of layered silicate, were treated with 0.1, 0.3, 1.0 and 3.0 M NaOH solutions at temperatures from 25 to 150 °C under autogenous pressure for 7 days. After the hydrothermal treatment, the transformation of the zeolites to phillipsite, hydroxyl‐sodalite and analcime was observed, depending on the temperature and NaOH concentration. The amounts of ammonium ions taken up into the hydrothermally‐treated zeolites were compared with those of the starting materials. The treated products, containing mainly phillipsite, took up twice the amount of ammonium ions as the starting materials. The maximum uptake of ammonium ions was 1.92 mmol g^?1. The number of ammonium ions taken up into phillipsite was equal to the number of Na⁺ ions released from phillipsite. These results indicate that the uptake of ammonium ions proceeds by an ion‐exchange mechanism with Na⁺ ions. Copyright © 2005 Society of Chemical Industry     

Structural changes in the endoplasmic reticulum of starfish oocytes during meiotic maturation and fertilization

The endoplasmic reticulum (ER) of live starfish oocytes was observed during meiotic maturation and fertilization. The ER was visualized by injection into the cytoplasm of an oil drop saturated with the fluorescent lipophilic dye DiI; DiI spread throughout the oocyte endoplasmic reticulum and the pattern was imaged by confocal microscopy. The ER in the immature (germinal vesicle stage) oocyte was composed of interconnected membrane sheets. In response to 1-methyladenine, the sheets of ER appeared to become associated with the yolk platelets, forming spherical shells. A few of these spherical shells could sometimes be seen in immature oocytes, but their number was much greater in the egg at the first meiotic spindle stage. At about the time that the first polar body formed, the spherical shells disappeared, and the ER returned to a form like that of the immature oocyte. The spherical shells did not reappear during the second meiotic cycle. During maturation, the ER also began to move; the movement was apparent by the time of germinal vesicle breakdown and continued throughout both meiotic cycles and in eggs with second polar bodies. When eggs at the first meiotic spindle stage were fertilized, the form of the ER changed. Within 1 min after sperm addition to the observation chamber, the circular cross sections of the spherical shells of the unfertilized egg ER were no longer distinct. At this point, the form of the ER could not be discerned with the resolution of the light microscope; however, the rate of spreading of DiI from an injected oil drop decreased, providing strong evidence that the ER had become fragmented. The ER remained in this form for several minutes and then gradually, the appearance of the ER and the rate of DiI spreading returned to be like those of the unfertilized egg. Injection of inositol trisphosphate caused a similar change in the ER structure. These results indicate that the ER is a dynamic structure, the form of which changes during oocyte maturation and fertilization.     

<Emphasis Type=Italic>In-Situ</Emphasis> Observations of Martensitic Transformation in Blast-Resistant Steel

A hybrid in-situ characterization system, which couples the laser scanning confocal microscopy (LSCM) with the time-resolved X-ray diffraction (TRXRD) measurement with synchrotron radiation, was used to characterize the microstructure evolution during heat-affected zone (HAZ) thermal cycling of high-strength and blast-resistant steel. The combined technique has a time resolution of 0.3 seconds that allows for high-fidelity measurements of transformation kinetics, lattice parameters, and morphological features. The measurements showed a significant reduction in the martensite start transformation temperature with a decrease in the prior austenite grain size. In addition, the LSCM images confirmed the concurrent refinement of martensite packet size with smaller austenite grain sizes. This is consistent with dilatometric observations. The austenite grain size also influenced the rate of transformation (df _m /dT); however, the measurements from the hybrid (surface) and dilatometric (volume) measurements were inconsistent. Challenges and future directions of adopting this technique for comprehensive tracking of microstructure evolution in steels are discussed.     

Direct Observation that Bainite can Grow Below MS

In situ simultaneous synchrotron X-ray diffraction and laser scanning confocal microscopy have confirmed that bainite in steels can grow below the martensite start temperature. This observation suggests that the formation curves for bainite in time-temperature-transformation diagrams should be extended below the martensite start temperature. Furthermore, the implication of this observation on the growth mechanism of bainitic ferrite is discussed.     

In situ observation of the formation of intragranular acicular ferrite at non-metallic inclusions in C–Mn steel

Intragranular acicular ferrite is regarded as a most desirable microstructure feature, in view of its strength and toughness, both in weld metals and in the heat-affected zone. This paper systematically investigated the effect of Ti addition on the evolution of intragranular acicular ferrite in the heat-affected zone of C–Mn steel. We also systematically studied the effects of austenite grain size, alloy content and the characteristic of inclusions on the formation of intragranular acicular ferrite. The nucleation and growth of intragranular acicular ferrite was directly observed by laser scanning confocal microscopy. Subsequently, microscopy analysis was used to quantitatively determine and distinguish the potent and inactive inclusions with respect to the nucleation of intragranular acicular ferrite. Finally, some possible reasons are given to explain the formation of intragranular acicular ferrite in the C–Mn steel.     

On the Excess Oxygen in Four-Layered Rock-Salt-Type Units of Modulated Thermoelectric Bi-Sr-(Co,Rh)-O Compounds

Excess oxygen exists in four-layered rock-salt (RS)-type units of modulated misfit-layered Bi-Sr-(Co,Rh)-O compounds, which consist of interpenetrating CdI₂-type (Co,Rh)O₂ and distorted four-layered RS-type block subsystems, which have two b-axes, i.e., b ₁ and b ₂, respectively. From carefully determined chemical contents and misfit ratios, p = b ₁/b ₂, two structural characteristics are concluded, namely, intermixing metal ions in the RS-type layers and excess oxygen δ in, or in the vicinity of, them. The chemical formulae are proposed as [(Bi_1−x (Co,Rh) _x )₂(Sr_1−y Bi _y )₂O_4+δ ] _p (Co,Rh)O₂. The valence states of␣cobalt and rhodium ions are close to 3.3+. These valence states are quite reasonable for good thermoelectric oxides, such as γ-Na_0.7CoO₂ and [Ca₂CoO₃]_0.62CoO₂. Excess oxygen would cause the undulated atomic arrangement.     

Microbial α-L-Rhamnosidases of Glycosyl Hydrolase Families GH78 and GH106 Have Broad Substrate Specificities toward α-L-Rhamnosyl- and α-L-Mannosyl-Linkages

α-L-Rhamnosidases (α-L-Rha-ases, EC 3.2.1.40) are glycosyl hydrolases (GHs) that hydrolyze a terminal α-linked L-rhamnose residue from a wide spectrum of substrates such as heteropolysaccharides, glycosylated proteins, and natural flavonoids. As a result, they are considered catalysts of interest for various biotechnological applications. α-L-rhamnose (6-deoxy-L-mannose) is structurally similar to the rare sugar α-L-mannose. Here we have examined whether microbial α-L-Rha-ases possess α-L-mannosidase activity by synthesizing the substrate 4-nitrophenyl α-L-mannopyranoside. Four α-L-Rha-ases from GH78 and GH106 families were expressed and purified from Escherichia coli cells. All four enzymes exhibited both α-L-rhamnosyl-hydrolyzing activity and weak α-L-mannosyl-hydrolyzing activity. SpRhaM, a GH106 family α-L-Rha-ase from Sphingomonas paucimobilis FP2001, was found to have relatively higher α-L-mannosidase activity as compared with three GH78 α-L-Rha-ases. The α-L-mannosidase activity of SpRhaM showed pH dependence, with highest activity observed at pH 7.0. In summary, we have shown that α-L-Rha-ases also have α-L-mannosidase activity. Our findings will be useful in the identification and structural determination of α-L-mannose-containing polysaccharides from natural sources for use in the pharmaceutical and food industries.     

Basic examination of membrane electrode assembly of proton exchange membrane fuel cell considering heat deterioration

The purpose of this research is to develop a standard preparation method for membrane electrode assemblies (MEAs). Therefore, the preparation method for multilayered MEAs with gas diffusion layers (GDLs) and the degree to which polymer membranes deteriorate by heating were studied. As a result, improvement of power density by making multi catalyst layers provides a solution to some problems found in thin polymer membranes. In addition, it was found that improving the diffusion of gas through two-layer GDLs in cathode (duct side: carbon paper, catalyst layer side: carbon cross) results in a cross leak reduction. Moreover, a making condition of MEAs was optimized by varying the temperatures used for the multi catalyst layers and two-layer GDLs. The analysis of heat deterioration of the Nafion membrane using X-ray photoelectron spectroscopy (XPS) indicates that the optimal hot press temperature is 130 °C.     

Soft X-ray Absorption and Photoemission Spectroscopy Study of Cobalt-Based Thermoelectric Oxides: \hbox{Ca}_3\hbox{Co}_4\hbox{O}_9, \hbox{Ca}_3\hbox{Co}_2\hbox{O}_6, and \hbox{Bi}_{2}\hbox{Sr}_{2}\hbox{Co}_2\hbox{O}_{y}

The electronic structures of Co-based potential thermoelectric (TE) oxides, including $\hbox{Ca}_3\hbox{Co}_4\hbox{O}_9$ and $\hbox{Bi}_{2}\hbox{Sr}_{2}\hbox{Co}_2\hbox{O}_{y}$ (y = 8 + δ) single crystals and polycrystalline $\hbox{Ca}_3\hbox{Co}_2\hbox{O}_6$ , have been investigated by employing soft x-ray absorption spectroscopy (XAS) and photoemission spectroscopy (PES). Co 2p XAS measurements show that Co ions are nearly trivalent ( $\hbox{Co}^{3+}$ ) in all of these Co-based TE oxides with a small mixture of $\hbox{Co}^{4+}$ ions in $\hbox{Bi}_{2}\hbox{Sr}_{2}\hbox{Co}_2\hbox{O}_{y}$ . Valence-band PES and O 1s XAS measurements show that the occupied Co 3d states are located at the top of the valence bands and that the lowest unoccupied states have the primarily Co 3d character, respectively. These findings suggest the importance of the Co 3d electronic structures in determining TE properties of these Co-based oxides.     

Possible role of dentin matrix in region-specific deposition of cellular and acellular extrinsic fibre cementum

The mechanism whereby a region-specific deposition of the two types of cementum (cellular cementum and acellular extrinsic fibre cementum) is regulated on the growing root surface was tested using bisphosphonate-affected teeth of young rats and guinea pigs. The animals were injected subcutaneously with 8 or 10 mg P x kg body weight(-1) x day(-1) of 1-hydroxyethylidene-1,1-bisphosphonate (HEBP) for 1 or 2 weeks. In rat molars, HEBP prevented mineralization of newly formed root dentin matrix and totally inhibited de novo deposition of acellular extrinsic fibre cementum. Instead, thick cellular cementum was induced on the non-mineralized root dentin surface, irrespective of the position of the root. In both animals, cellular cementum was also induced on the non-mineralized surface of root analogue dentin in HEBP-affected incisors, where only acellular extrinsic fibre cementum is deposited under normal conditions. In normal rat molars, dentin sialoprotein (DSP) was concentrated along the dentin-cellular cementum border, but not that of dentin and acellular extrinsic fibre cementum. In HEBP-affected rat incisors, DSP was shown to penetrate through the non-mineralized dentin into the surrounding tissues, but not through the mineralized portions. These data suggest that, at the site of cellular cementum formation, putative inducing factors for cellular cementum might diffuse into the periodontal space through the newly deposited mantle dentin matrix before it is mineralized. At earlier stages of root formation, mantle dentin might mineralize more promptly not to allow such diffusion. The timing of mineralization of mantle dentin matrix might be the key determinant of the types of the cementum deposited on the growing root surface.