Effects of metal elements on beta-hexosaminidase release from rat basophilic leukemia cells (RBL-2H3).

Immediate allergy is caused by a chemical mediator released from basophile and mast cells via cell degranulation due to reaction between an immunoglobulin E (IgE) antibody, bound with the IgE receptor on the cell membrane, and an antigen. The present authors have established a new method for assaying the enzyme activity of beta-hexosaminidase as an index of chemical mediator release. Using cultured cells instead of conventional methods based on histamine release from mast cells, the present method permits highly accurate mass screening since it uses a well-established cell line of rat basophilic leukemia cells (RBL-2H3). The effects of metal elements on immediate allergic reaction were evaluated using a newly developed assay system. A total of 38 metal elements were investigated for effects on immediate allergic reactions in vitro. These elements were classified by five types on the basis of action on beta-hexosanimidase release: 1) those which showed very strong inhibitory action, such as ZnCl2 and ZrCl4, 2) those which showed relatively strong inhibitory action, such as CdCl2 and CuCl2, 3) those which showed relatively weak inhibitory action, such as CoCl2 and Pb(NO3)2, 4) those which showed neither inhibitory nor promoting action, such as MnCl2 and SrCl2, and 5) AgNO3, which alone showed promoting action.     

Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐Molybdate(II) Anions: Synthesis,Spectroscopy, and Density Functional Theory Calculations

Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐molybdate‐(II) anions, [fac‐M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo), which are novel weakly coordinating anions that contain a metal carbonyl/nitrosyl moiety, have been generated in fluorosulfonic acid and completely characterized by multinuclear NMR, IR, and Raman spectroscopy as well as ESI mass spectrometry. ESI MS measurements performed for the first time on a superacidic solution system unambiguously reveal the formation of the monoanionic, mononuclear W and Mo complexes formulated as [M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo). Multinuclear NMR spectroscopic studies at natural abundance and ¹³C and ¹⁵N enrichment clearly indicate the presence of one CO ligand, two equivalent NO ligands, and two types of nonequivalent SO₃F^? groups in a 2:1 ratio. The IR and Raman spectra reveal that the two equivalent NO ligands have a cis conformation, thus indicating a fac structure. Density functional calculations at the B3LYP level of theory predict that these anions have a singlet ground state (¹A′) with a C_s symmetry along with C–O and N–O vibrational frequencies that are in agreement with the experimental observations. Mulliken population analysis shows that the monovalent negative charge is dispersed on the bulky sphere, the surface of which is covered by all the negatively charged O and F atoms with charge densities much lower than SO₃F^?, suggesting that [fac‐M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo) are weakly nucleophilic and poorly coordinating anions.     

High n-value phases in the complex bismuth oxides with layered structure,Bi2CaNan−2NbnO3n+3

Complex bismuth oxides with layered structure are prepared with a series of compositions in the system Bi₂CaNb₂O₉-NaNbO₃. It is found by X-ray powder diffraction that each compound is composed of more than two phases, which are described by a formula Bi₂CaNa_n?2Nb_nO_3n+3, e.g., in the sample with the nominal composition Bi₂CaNb₂O₉ · 8NaNbO₃, the phases with n = 6 to 8 appear predominantly. These phases are closely intergrown to each other. Moreover, high-resolution electron microscopy reveals that microsyntactic intergrowth frequently occurs in the phases with n > 5. The occurrence of the latter intergrowth is explained in terms of the bond length obtained.     

Crystal structures of V3S4 and V5S8

Crystal structures of the ordered phases of V₃S₄ and V₅S₈ were refined with single crystal data. Both are monoclinic. Chemical compositions, space groups and lattice constants are as follows: VS_1.47, $\text{I2}\text{m}$ (No. 12), a = 5.831(1), b = 3.267(1), c = 11.317(2)Å, β = 91.78(1)° and VS_1.64, $\text{F}\text{2}\text{m}$ (No. 12), a = 11.396(11), b = 6.645(7), c = 11.293(4), Å, β = 91.45(6)°. In both structures, short metal-metal bonds were found between the layers as well as within them. In comparison with the structure of Fe₇S₈, the stability of NiAs-type structure was discussed based on the detailed metal-sulfur distances.     

DNA topology on an increase in positive writhing number of DNA: conformation changes in the time course of cis-diamminedichloroplatinum(II)-DNA adducts

We show that the topological significance of the gel mobility of cis-diamminedichloroplatinum(II) (DDP)-closed circular DNA (ccDNA) adducts decreases with reaction time, until a point at which it joins relaxed DNA, and that the mobility of the adducts increases again. There is no relationship between the relative length of the adducts and the gel mobility. Although the significance of the decrease of gel mobility is due to the unwinding of cis-DDP-DNA (or trans-DDP-DNA) adducts, the conformational significance of the subsequent increase in mobility is unclear. To elucidate the conformational significance for unwinding of the adducts, we measured the writhing number (Wk) of the adducts using electron microscopy and analyzed the topological states of cis-DDP (or trans-DDP) adducts based on the White rule, Lk=Wk+Tk. Where, Lk and Tk represent the linking and twisting number in the ring, respectively. From the data, we found that the Wk of cis-DDP-ccDNA adducts in comparison with trans-DDP-ccDNA adducts increases from a negative to a positive number with time. This suggests that cis-DDP plays a role in the change of the topological state of ccDNA. In the abstraction of platinum from the adducts with CN- ion, the differences in both topological states may explain why Pt in trans-DDP is abstracted more easily than in cis-DDP. To explain the abstraction of Pt ion, we also discuss the findings based on the thermodynamic cycle in a intermolecular crosslink model Pt(NH3)2(guanine)2(2+)-->Pt(CN)4(2-) using the Pt parametrized PM3 method.     

Polyoxymethylene prepared by γ-ray-induced polymerization of tetraoxymethylene single crystal

Summary In order to prepare a large single crystal, tetraoxymethylene recrystallized by distilled water adjusted to pH 8 was sealed in an ampoule at a reduced pressure of 1 mm Hg and was crystallized in a furnace with the temperature gradient of 6 °C/cm. The lowering rate of the ampoule was required to be 6 cm/day for preparing the single crystal with 1 cm diameter and to be 3 cm/day for one with 2 cm diameter. The optimum angle at the pointing end of the ampoule, where a seed crystal is formed, was about 40°. The b-axis of the obtained single crystal was parallel to the direction of the crystal growth i. e. the wall of the ampoule. It was polymerized byγ-ray under conditions which prevent the growth of the twin crystal. The obtained polyoxymethylene was porous, because the polymerization yield of 100% could not be attained. However, it was so tough that a specimen for measurements could be cut down by a diamond cutter. Its fiber axis was parallel to the direction of the wall of the ampoule. It did not contain the so-called amorphous regions, although it did contain defects. It was characterized with the extremely high orientation of the polymer chains.

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Zusammenfassung Zur Pr?parierung gro?er Einkristalle wurde rekristallisiertes Tetraoxymethylen in destilliertem Wasser von p_H 8 in eine Ampulle bei einem reduzierten Quecksilberdruck von 1 mm eingefüllt und in einem Ofen mit einem Temperaturgradienten von 6 °C/cm kristallisiert. Die Abkühlgeschwindigkeit der Ampulle betrug etwa 6 cm/Tag für die Pr?paration eines Einkristalls mit 1 cm ? und 3 cm/Tag für einen solchen mit 2 cm ?. Der optimale Winkel am spitzen Ende der Ampulle, wo der Keimkristall gebildet wird, betrug etwa 40°. Dieb-Achse des Einkristalls war parallel zur Wachstumsrichtung, d. h. zur Wand der Ampulle. Der Kristall wurde durch R?ntgenstrahlen polymerisiert unter Bedingungen, die das Wachsen eines Zwillingskristalls vermeiden. Das erhaltene Polyoxymethylen war por?s, doch konnte eine Polymerisationsausbeute von 100% nicht erhalten werden. Doch war der Einkristall so z?h, da? für Messungen eine Probe mit dem Diamantschneider abgeschnitten werden konnte. Die Faserachse war parallel zur Wandrichtung der Ampulle. Das kristalline Material enthielt keine sogenannten amorphen Bereiche, allerdings Defekte. Es war durch extrem hohe Orientierungen der Polymerketten charakterisiert.

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We are greatly indebted to Dr.Y. Miyake of Mitsui Toatsu Co., Ltd. for providing the tetraoxymethylene. Thanks are to due Dr.M. Nishii of Osaka Laboratories, Japan Association for Radiation Research on Polymer for the radiation polymerization, to Mr.T. Tsukihara for the X-ray measurement, and to Mrs.H. Tanaka for the help with the electron microscopy. We are also grateful to Prof.S. Seki for offering the use of differential scanning calorimeter.     

New hydroxyl protecting groups of a safety-catch type removable by reductive acidolysis.

New hydroxyl protecting groups of a safety-catch type, i.e., 4-methylsulfinylbenzyl-oxycarbonyl (Msz) group for Tyr and 4-methylsulfinylbenzyl (Msob) ether for Thr, have been developed. O-Msz and O-Msob groups are stable under both acidic and basic conditions and can be removed by a one-pot reaction involving reductive acidolysis using tetrachlorosilane-trifluoroacetic acid (TFA)-scavengers. Using these new protecting groups, a 17 residue-peptide, gamma-endorphin, was successfully synthesized by the efficient solid phase method.     

Cationic polymerization of cyclic olefins

The polymerization and the polymerizabilities of indene, benzofuran, and 1,2-dihydronaphthalene are discussed from the point of view of ring strain, ring stabilization, and steric hindrance in the transition state. Monomer reactivities of these olefins were estimated from copolymerization with styrene and from the rate of addition of iodine bromide in acetic acid. Rates and degrees of polymerization are compared with monomer reactivities and resonance energies of indene, 1,2-dihydronaphthalene, and benzofuran as a measure of ring strain and stabilization. It is found that indence is 1.5–2.0 times more reactive than styrene. This high reactivity of indene is attributed to the ring strain in the monomer state and to the low amount of steric hindrance in the transition state of the coplanar five-membered cyclic olefin. 1,2-Dihydronaphthalene is strained and therefore reactive, but propagation to higher molecular weight products is impeded due to the steric hindrance. The reactivity of benzofuran is decreased by conjugative stabilization of C?C double bonds at the reaction site.     

Studies on Fe complexes produced by yeast. IV. Mechanism of Fe transport from an Fe(II)-oligosaccharide complex across the mucosal membrane of the rat intestine

The mechanism of Fe transport across the rat duodenal membrane from an Fe(II)-oligosaccharide complex (designated B1-c) produced in wine by yeast and showing high hematopoietic activity in rats was examined. The Fe uptake from B1-c by brush border membrane (BBM) vesicles isolated from the rat intestine was based mainly on the Fe binding to membrane components which were suggested to be inside the vesicles. Evidence that Fe was transported into the vesicles by a special transport system other than simple diffusion was obtained by observing saturation kinetics under conditions of isotope exchange, and temperature and pH dependence. This Fe uptake was not inhibited by any metal ions tested, including inorganic Fe(II), and the BBM vesicles from the duodenum had a higher Fe uptake than those from the other parts of the small intestine. Furthermore, the BBM vesicles isolated from rats with Fe deficiency showed a significantly increased Fe uptake. The Km value for B1-c uptake was 0.16 mM, lower than the values for FeSO4 and ferrous ascorbate. These results suggest that a special transport system selective for B1-c may be present on the mucosal membrane. B1-c was taken up by the BBM vesicles in the form of Fe-oligosaccharide complex. From the preloaded vesicles, B1-c was released temperature- and pH-dependently.(ABSTRACT TRUNCATED AT 250 WORDS)