福岡県飯塚市古屋敷の蛇紋岩には,多くの炭酸塩鉱物が脈としてみられる。その中に紫色,白色,褐色のハイドロタルサイト族鉱物が産出する。そのうちの紫色のもの,および比較のためにオーストラリアタスマニア州Dundas産のスティヒタイトについて観察,分析を行った。古屋敷の紫色のハイドロタルサイト族鉱物はスティヒタイトであり,苦灰石脈中に取り込まれた蛇紋岩中のクロム鉄鉱の周囲に薄板状で産出する。化学組成はMg_6.09(Cr_1.55Fe_0.39)CO₃()

16

・4H₂Oであり,Dundas産のスティヒタイトMg_6.07(Cr_1.17Fe_0.62Al_0.07Si_0.06)CO₃(

OH

)

16

・4H₂O と比べてクロムの割合が多かった。また,X線回折パターンは,３Rのポリタイプを示した。

抄録全体を表示

Eighty-one fresh isolates of Pseudomonas pseudomallei from melioidosis patients were subjected to the analysis for the fatty acid composition by gas-liquid chromatography (GLC) and pH-dependent pattern of nonspecific phosphatase activity. All the test strains were identical in the GLC profile showing the three peaks of characteristic hydroxy acids (3-OH 14: 0, 2- : 0, 3- : 0) and the two prominent peaks of cyclopropane acids (17: 0 Δ, 19: 0 Δ) . They had also basically the same pH-dependent curves of the enzymatic activity with paranitrophenyl phosphate as substrate, showing two to three peaks or shoulders only in the acidic side of the curve. These two biochemical characteristics could differentiate P. pseudomallei distinctly from P. aeruginosa, but not from P. cepacia.

抄録全体を表示

Corrosion performance of zinc coatings containing aluminum in excess of 5% was assessed in modified salt-spray tests. X-ray diffraction studies indicated that the corrosion products consisted mainly of simonkolleite Zn₅(OH)₈Cl₂·H₂O, hydrozincite Zn₅(OH)₆(CO₃)₂, and zinc aluminum carbonate hydroxide hydrate Zn₆Al₂()

16CO₃

·4(H₂O). The content of Zn₆Al₂(

OH

)

16CO₃

·4(H₂O) in the corrosion product increased as the aluminum content in the coatings increased. SEM-EDX analyses revealed that the microstructural features formed by the primary aluminum-rich α-phase frequently corroded first and at a faster pace than the zinc-rich β-phase in these coatings. The volume fraction and morphology of the zinc-rich β-phase existing in the coatings as degenerated eutectic are the two main factors which determine the corrosion resistance of Zn–Al coatings under development. The corrosion resistance of coatings peaked at about 12% Al in this study.

抄録全体を表示

For the classical solution synthesis of human epidermal growth factor (h-EGF), four protected peptide derivatives, Boc-Lys (Cl-Z)-Trp-Trp-Glu (OcHex)-Leu-Arg (Tos)-OBzl (5), Boc-Glu (OcHex)-Arg (Tos)-Cys (MeBzl)-Gln-Tyr (Br-Z)-Arg (Tos)-Asp (OcHex)-Leu-OH (13), Boc-Tyr (Br-Z)-Ile-Gly- (), and Boc-Cys (MeBzl)-Asn-Cys (MeBzl)-Val-Val-Gly-OH (22) were synthesized to build up the sequence corresponding to 31-53.

抄録全体を表示

Some clay minerals are used and expected as barrier materials for engineering and in nature. Hydrotalcite, Mg₆Al₂[()

16

|CO₃]4H₂O and a kind of LDH (layered double hydroxides), is one of the most effective candidates for the anion adsorbents and the barrier. In this study, the behavior of hydrotalcite was investigated by means of the molecular dynamics method. Cl⁻ and I-hydrotalcite − water systems were simulated for various mineral/water ratios. The structure and dynamic properties are predicted. Water at the surface of hydrotalcite shows the electric double layer composed of Stern layer of one H₂O molecular layer thickness and large self-diffusion coefficient of H₂O and diffusion layer of 2.5 nm thickness at the interface.

抄録全体を表示

Strain IAM 14839, isolated from activated sludge in Japan, forms a visible floc and grows in the flocculated state. This bacterium is Gram-negative, rod-shaped, strictly aerobic and highly motile with a single polar flagellum. Both oxidase and catalase activities are positive. No growth was observed on sugars. The strain can grow at 20°C, but does not grow at 37°C. The G+C content of DNA is 66.3 mol% and Q-8 is the major quinone. The major cellular fatty acids are 16:1ω7c, 16:0, 18:1ω7c, 2 :0, 3OH 10:0. The 16S rDNA sequence analysis indicated that the bacterium clustered within the genus Comamonas. On the basis of the phylogenetic analysis and phenotypic properties, it is proposed that the strain IAM 14839^T be classified in a novel species of the genus Comamonas, Comamonas badia sp. nov. The type strain is IAM 14839^T (=KCTC 12244^T).

抄録全体を表示

 A tephra bed named CB2038 was found at a depth of 2038.26-2038.21 m in a boring core sample (hereafter called Chiba core) drilled at Chiba City, east of Tokyo Bay. The calcareous nannofossil assemblage from CB2038-bearing siltstone is characterized by the presence of small (< 3 μm) gephyrocapsids and Calcidiscus macintyrei, and the absence of discoasters, suggesting that CB2038-bearing strata correspond to the Ohara to the lower Kiwada formations (lower Pleistocene) exposed on the Boso Peninsula. Possible candidates to be correlative with CB2038 are

A, B in the Ohara Formation, and Kd48.2, Kd48.1, Kd48, and Kd40 in the lowermost Kiwada Formation, because of the similarity of the shapes of glass shards and heavy mineral composition (hornblende > orthopyroxene). Among these tephra beds, Kd48 was considered the best candidate to be correlative with CB2038 based on refractive index, and major and trace element compositions of glass shards. Kd48 identified from deep underground near Tokyo Bay would make a significant contribution to the subsurface stratigraphy of basement strata around the Tokyo metropolitan area.

抄録全体を表示

Composites of smectite / layered double hydroxide (LDH) were synthesized by various methods and their porous properties and microstructures examined. Commercial saponite and co-precipitated LDH [Mg₆Al₂(CO₃)()

16

-4H₂O] powders were used. Composites prepared by dry mechanical mixing, wet mechanical mixing and soft-chemical processing were characterized by XRD, FT-IR, XPS, SEM, TEM, and N₂ adsorption. The specific surface areas of the samples were intermediate between those of LDH and saponite. The value for the dry milled sample (167 m²/g) was smaller than for the other samples (about 250 m²/g). The pore size distributions of the saponite / LDH composites differ from those of the saponite and LDH, the peaks ranging from 1nm to 30nm according to the synthetic method. The resulting porous properties depend on laminating structure. Dry milling was the most effective method for modifying porous properties of the composites.

抄録全体を表示

In order to clarify the physiological significance of stereospecificities of peroxisomal multifunctional enzyme (MFE) type 1 (MFE1) and MFE2, we developed a chiral separation analysis for 3-hydroxyacyl-CoA using high performance liquid chromatography (HPLC) equipped with a chiral separation column. To demonstrate the utility of this technique, we cloned the hydratase domain from wild-type human MFE2 hydratase (MFE2Hwt) and expressed it as a GFP-tagged protein (GFP-MFE2Hwt) in Escherichia coli (E. coli). GFP-MFE2H was purified by diethylaminoethyl (DEAE) Sephacel from an E. coli sonication solution. As anticipated, we observed the formation of 3R-hydroxyhexadecanoyl-CoA (3R---CoA) on the HPLC chromatogram after incubating trans-2-enoyl-CoA (16eno-CoA) with GFP-MFE2Hwt. GFP-MFE2Hwt was readily purifiable and could be assayed because of its traceability. We used site-directed mutagenesis to construct GFP-MFE2H variants corresponding to 17 reported MFE2H missense mutations and measured their hydratase activities using our HPLC method. Hydratase activity was completely lost or markedly decreased in the same variants corresponding to MFE2H mutations in patients with D-bifunctional protein (DBP) deficiency type II. On the other hand, the nonpathological variants did not markedly affect hydratase activity.

抄録全体を表示

高知市周辺の蛇紋岩にはブルサイトとともにハイドロタルサイト族鉱物が比較的よく伴われる。X線的には7.7,7.8,8.0Åの3種の底面間隔が確認され,これらの平均化学組成としてpyroauriteに相当する(Mg_6.20Ni_0.13Fe³⁺_1.67)()

16

(CO₃)_0.84・4H₂Oが得られた。これらの重金属交換実験ではCr,Ni,ZnよりもCuにおける交換率が最も高く反応後の底面間隔の増大からすれば7.8,8.0Åの2種が選択的に交換反応に与っている。

抄録全体を表示

Atmospheric corrosion of hot-dip Zn-6%Al-3%Mg alloy coated steel sheet after 5 years of exposure in a severe marine and a rural sites have been investigated compared with Zn-0.2%Al and Zn-4.5%Al-0.1%Mg alloy coated steel sheets.
The corrosion resistance of Zn-6%Al-3%Mg alloy coated steel sheet is more superior than that of Zn-4.5%Al-0.1%Mg alloy coated steel sheet in both exposure sites. An extensive study using XRD and TEM revealed that the corrosion products consisting of amorphous, finecrystal Zn₅(OH)₈Cl₂·H₂O and Zn₆Al₂()

16CO₃

·4H₂O are formed on Zn-6%Al-3%Mg alloy coated steel sheet after 1 year of exposure in a severe marine site. Even after 5 years of exposure the formation of zinc oxide, which have little protective action for coatings, is suppressed on Zn-6%Al-3%Mg alloy coated steel sheet.
It is concluded that the surface of Zn-6%Al-3%Mg alloy coated steel sheet is covered with the protective corrosion products in the early stage of exposure, resulting in the remarkably improvement of atmospheric corrosion resistance.

抄録全体を表示

We present the first report of okhotskite in a lawsonite–blueschist–subfacies metachert of the Hakoishi subunit, Kurosegawa Belt, Kyushu, Japan, which was metamorphosed at peak temperatures and pressures of 200–300 °C and 0.6–0.8 GPa. This okhotskite–bearing assemblage is particularly notable because it formed at higher pressures than that of previously documented okhotskite with available pressure estimations. Textural relationships indicate that okhotskite formed during peak metamorphism in equilibrium with piemontite, Na pyroxene, magnesioriebeckite, braunite, and hematite. Okhotskite shows a significant variation in Fe:Mn ratio (Fe_tot/Mn_tot = 0.13–0.56) and a following average empirical formula; (Ca_7.62Mn²⁺_0.16)_Σ7.78(Mn²⁺_2.71Mg_1.29)_Σ4.00
(Mn³⁺_4.13Fe³⁺_2.26Al_1.36V³⁺_0.23Ti_0.02)_Σ8.00Si_11.86O_44.02(

)

16.98

. Raman spectra of okhotskite are reported for the first time and show characteristic peaks at 362, 480, and 563 cm⁻¹. The stability relationships between okhotskite and other Mn–bearing minerals, such as piemontite, sursassite, spessartine, braunite, and Mn–bearing lawsonite, are examined using a revised Schreinemakers’ analysis. The obtained petrogenetic grid provides tight constraints on the P–T relationship of natural mineral assemblages observed in Mn–bearing cherts within epidote–blueschist–grade and lawsonite–blueschist–grade. Furthermore, this petrogenetic grid predicts that the assemblage of okhotskite and Mn–bearing lawsonite should be stable at higher pressures. The higher–pressure stability suggests that highly oxidized Mn–bearing metacherts can transport water and buffer oxygen in the deeper parts of subduction zones, given that okhotskite and Mn–bearing lawsonite contain high water contents (6.9 and 11.3 wt% H₂O, respectively) and trivalent manganese.

抄録全体を表示

Some discussions about the mechanism of the unexpected severe impingement corrosion of condenser tubes were made in relation to hydrotalcite. It was elucidated experimentally that hydrotalcite is the initial corrosion product of Aluminum Brass in the natural sea water. Even if iron rich protective films are formed on hydrotalcite, they will be broken quite easily by the collision of foreign bodies with smaller energy in the sea water. This will increase the possibility of corrosion. The most important countermeasure is to supress the initial corrosion of condenser tubes by the effective ferrous ion dosing and to prevent hydrotalcite formation. It was pointed out that more attension should be paid to hydrotalcite from the standpoint of corrosion engineering of condenser tubes.

抄録全体を表示

Tamaite, (Ca, K, Ba, Na)₃₋₄Mn₂₄(Si, Al)₄₀(O, OH)₁₁₂·21H₂O, the Ca-analogue of ganophyllite, is found from the Shiromaru mine, Okutama, Tokyo, Japan. It is monoclinic, P2₁/a, a=16.64(1), b=27.11(2), c=25.35(2)A, β=98.74(7)°, Z=4. The strongest lines in the X-ray powder diffraction pattern are 12.6 (vvs) (002), 3.46 (m) (027), 3.13 (s) (008), 2.84 (s) (38 -2), 2.69 (vs) (38 -4), 2.60 (s) (602), 2.46 (s) (60 -6), 2.38 (m) (604), 1.623 (m) (98 -2), 1.609 (m) (3 10 11). Electron microprobe and Karl-Fischer analyses gave SiO₂ 41.23, Al₂O₃ 7.79, FeO 0.16, MnO 35.17, MgO 0.23, CaO 1.94, BaO 2.03, Na₂O 0.34, K₂O 0.82, H₂O 11.07, total 100.78 wt%, and lead to the empirical formula, (Ca_1.65K_0.83Ba_0.63Na_0.53)_Σ3.64(Mn_23.71Mg_0.27Fe_0.11Al_0.12)_Σ24.21(Si_32.81Al_7.19)_Σ40.00 O_95.27()

16.73

·21H₂O on the basis of O=133. It is transparent and colorless to pale yellowish brown in color with vitreous to pearly luster. The streak is white and cleavage perfect on {001}. The Mohs' hardness is about 4. The measured and calculated densities are 2.85(5) g/cm³ and 2.83 g/cm³, respectively. It is colorless in thin section and optically biaxial negative with β=1.612(2) and 2 V<15°. It occurs as veinlets up to 1.5 mm thick composed of micaceous platy crystals under 0.5 mm in diameter and as spotted crystals in celsian-barian orthoclase veinlets cutting host rocks of metamorphosed manganese ore deposit. The mineral is considered to be formed during later stage activity of low grade metamorphism.

抄録全体を表示

Many advances have been made recently in the methods for analysis of steroids by gas liquid chromatography (GLC). These advances comprise the developments of new phases, new reagents and a new high-sensitivity detector (Ni-63). New silylation reagents, BSA (bistrimethylsilylacetamide), TMSI (trimethylsilylimidazole), chloromethyldimethylsilane and others, are very useful for steroid analysis.
Trimethylsilylation of steroids, especially of corticosteroid methyloxime was investigated by using these reagents. TMSI is a stronger silylation reagent than BSA. Trimethylchlorosilame (TMCS) is an effective catalyst for silylation. Hydroxy groups on 3-, 20-, 21-, and other sterically non-hindered groups are trimethylsilylated with BSA for 10-30 minutes at room temperature. Sterically hindered hydroxy groups, such as 11-, 12-, and 17 positions, are trimethylsilylated with BSA-TMCS or TMSI-TMCS. Methyloxime derivatives of adrenocortical steroids and their metabolites can be analyzed by GLC as a single peak after trimethylsilylation of non-hindered hydroxy groups or all of the hydroxy groups. Thus, all neutral urinary steroids, 17-KS, pregnane derivative, 17-OHCS, and others, may be analyzed simultaneously without any preliminary separation by the temperature programmed method.
Correlations between the urinary steroids and diseases may be studied most effectively by using this steroid pattern method. In the urine of a new born infant, as shown in Fig. 1, 16-OH-17-keto, 16-keto-17-, , 17-diOH-androsten-3β-o1, 21-OH and 16-OH-pregnenolone were found, but not so-called 17-OHCS. In case of adrenocortical cancer, a different urinary steroids profil from that of a normal person was obtained. As shown in Fig. 2, Δ⁵-pregnendiol, Δ⁵-pregnenetriol, 16-OH and 21-OH pregnenolone were found.
Steroids and steroid derivatives are best characterized in terms of methylene unit (MU) values. These are determined by temperature programmed separations using n-paraffins as reference compounds. MV-Values of about 60 kinds of urinary steroids were determined on OV-1 and OV-17.
Cholesterol and cholesterol ester, C₁₆ and C₁₈ ester, in serum can be determined simultaneously by GLC by using a short column and temperature programmed method from 200° to 300°C. Free and ester forms of cholesterol in the serum patients with various disease were determined by this method. This is useful for the determination of the function of liver, pancreas, and thyroid gland. In the case of some brain tumor and pancreas cancer, no ester form as observed in the serum.

抄録全体を表示

Chlorites from Byrapur, Bhaktarhalli and Tagadur mine areas in Nuggihalli schist belt, belonging to the greenstone belt of South India, were investigated for determining the crystallochemical characteristics of these product phases arising from low-grade metamorphism of ultramafic rocks of komatiitic lineage. The analytical equipments used for such investigation were EPMA, ⁵⁷Fe Mössbauer spectroscopy, XRD and IR. The physicochemical properties of these chlorites are found to lie between aluminian clinochlore and clinochlore varieties. The cell parameters calculated from major XRD peaks reveal the crystallographic parameters, the range of which are: for aluminian-clinochlore, a=5.3027 to 5.3172 Å, b=9.2721 to 9.2796 Å, c=14.3496 to 14.4078 Å, β=97.984° to 98.085°, V=700.9790 to 701.5324 ų; for clinochlore, a=5.2815 to 5.3495 Å, b=9.1897 to 9.2502, c=14.1634 to 14.2814 Å, β=95.200 to 96.554°, V=692.8576 to 695.8528 ų; and for Cr-clinochlore, a=5.3310 to 5.3190 Å, b=9.1303 to 9.2790Å, c=14.3395 to 14.3370 Å, β=94.589° to 97.670°, V=695.7210 to 701.2580 ų.
In all the samples octahedral sites are mostly occupied by Al^VI, Fe and Mg. The chemical variation is largely controlled by the isomorphous replacement of Mg²⁺by Al^VI which has effected the Fe²⁺-Mg²⁺ substitution. The shrinkage resulting from octahedral Al³⁺ substitution is balanced by the expansion effected by Fe-Mg substitution. The octahedral site (M4) occupied by Al³⁺ is smaller than when occupied by Mg²⁺ or Fe²⁺. The initial Al3+ occupancies of the two M4 sites change with progressive oxidation and metamorphism.
The Mössbauer spectrum of a chlorite sample depicts five symmetric doublets for iron, three of which are assigned to Fe²⁺ at cis and trans positions of talc layer, and in brucite layer; the other two are assigned to Fe ³⁺ at trans position and tetrahedral site. The iron distribution over the octahedral site signifies oxidation of Fe²⁺ only at trans position, while at the cis and brucite positions Fe²⁺ remains unaffected. The Mössbauer results of this chlorite suggest the Fe³⁺ occupancy in octahedral sites was the result of oxidation (following chloritisation) and the distribution of other cations in the other two sites remained unaffected.
The oxidation of chromite grains would release Cr³⁺ and Al³⁺ from theoctahedral sites and these released cations would react with contiguous serpentine (antigorite) to form Cr-clinochlore. The Al³⁺ content of Cr-clinochlore is seen to be distinctly related to the degree of oxidation of the associated chromite-a greater degree of oxidation of chromite is related to a higher Al³⁺ content with a concomitant lowering Mg²⁺ and Si⁴⁺ contents in the associated Cr-clinochlore. Using the geothermometry of Xie et al.(1997) the temperature of formation of these chlorites (Al^IVranging from 1.398 to 2.540) are found to lie between 263 and 463°C; this wide range of temperature may arise from polymetamorphism experienced by the area.

抄録全体を表示

島根半島三津産パンペリー石におけるFeの酸化数と6配位席における分布，及びそれらの結晶構造に与える影響をメスバウアー法とX線リートベルト法を用いて検討した．その結果，三津産パンペリー石の化学式は(Ca7.98Na0.06)WΣ8.04(Fe2+0.88Mg0.67Fe3+0.79Al1.64)XΣ3.98(Al5.67Fe3+2.34)YΣ8.01Si12.00O39.94().06となり，したがって本鉱物はferrian pumpellyite-(Al)である． Al＝Fe3+置換によるY席の膨張が格子定数, 平均原子間距離に大きな影響を与えるのに対し，X席におけるイオン置換の影響は顕著ではなく，結晶構造全体に与える影響も小さいことが判明した．Y席はFe3+の増加により膨張し，より秩序的な八面体に近づくため変形度が減少する．

抄録全体を表示

The mechanism of anion-exchange selectivity of the layered double hydroxides (LDHs) and the LDHs-dyes hybrid materials with molecular detection ability has been investigated in this paper. In the part of mechanism elucidation of anion-exchange selectivity of LDHs, the structural features of LDHs obtained by synchrotron X-ray diffraction and the chemical states of anion species and hydration water molecules in the interlayers of LDHs obtained by Raman spectroscopy and ¹⁷O solid-state NMR have been clarified. Moreover, synchrotron radiation X-ray diffraction in-situ measurement system at SPring-8 was assembled for measuring the crystal structure changes during anion exchange reactions and it was found that the dynamic structure changes of LDHs was successfully measured. In the part of dyes-LDHs hybrid materials with molecular detection ability, it was found that LDHs modified with zinc-porphyrin and amphiphilic molecules can detect pyridine molecules in water at very low concentrations (on the order of nmol/L).

抄録全体を表示

Enthalpies of hydration of low-temperature hydrotalcite(HT) metaphases have been measured by means of the adiabatic water-vapor absorption calorimeter. The metaphases were characterized by the Mg/Al ratio of 3 : 1 and CO₃²⁻ interlayer group. The hydration heat for HT-B (partially dehydroxylated HT with bidentate bonded CO₃²⁻) is 2-3 times larger than that of HT-D (dehydrated HT), if they are treated at the same dehydration temperature. Large absolute values of hydration heat, namely 398±4 and 508±10Jg⁻¹, were obtained for the HT-B at respective low dehydration temperatures, 70 and 110°C . This may promise the HT-B to be a new prospective heat exchanger usable at relatively low temperatures.

抄録全体を表示