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.     

Umbelliferose Isolated from Cuminum cyminum L. Seeds Inhibits Antigen-Induced Degranulation in Rat Basophilic Leukemia RBL-2H3 Cells

Cuminum cyminum L. (cumin) is an annual plant of the Umbelliferae family native to Egypt. We previously showed that the aqueous extract of cumin seeds suppresses degranulation by downregulating the activation of antigen-induced intracellular signaling molecules in rat basophilic leukemia RBL-2H3 cells. However, the active substances in the extract have not yet been identified. Accordingly, herein, we aimed to ascertain the water-soluble substances present in cumin seeds that inhibit degranulation, which led to the identification of umbelliferose, a characteristic trisaccharide present in plants of the Umbelliferae family. Our study is the first to reveal the degranulation-suppressing activity of umbelliferose, and quantification studies suggest that cumin seed powder contains 1.6% umbelliferose. Raffinose, an isomer of umbelliferose, was also found to significantly suppress antigen-induced degranulation, but less so than umbelliferose. Both umbelliferose and raffinose contain sucrose subunits in their structures, with galactose moieties bound at different sites. These differences in structure suggest that the binding of galactose to the sucrose subunit at the α1-2 bond contributes to its strong degranulation-inhibiting properties.     

Synthetic Studies on Sialoglycoconjugates 22: Total Synthesis of Tumor-Associated Ganglioside,Sialyl Lewis X1

ABSTRACT

The first total synthesis of tumor-associated glycolipid antigen, sialyl Lewis X is described. Glycosylation of 2-(trimethylsilyl)ethyl O-(2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (1) with methyl 2,3,4-tri-O-benzyl-1-thio-β-L-fuco-pyranoside (4) gave the α-glycoside (5), which was converted by reductive ring-opening of the benzylidene acetal into the glycosyl acceptor (6). Dimethyl(methylthio)sulfonium triflate-promoted coupling of 6 with methyl O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside (7) afforded the desired hexasaccharide 8 in good yield. Compound 8 was converted into the α-trichloroacetimidate 11, via reductive removal of the benzyl groups, O-acetylation, removal of the 2-(trimethylsilyl)ethyl group, and treatment with trichloroacetonitrile, which, on coupling with (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octa-decene-1,3-diol (12), gave the β-glycoside 13. Finally, 13 was transformed, via selective reduction of the azide group, condensation with octadecanoic acid, O-deacylation, and hydrolysis of the methyl ester group, into the title compound 16.     

Communication: Synthetic Studies on Sialoglycoconjugates 110: Efficient Assembly of α-Linked Tetrameric Sialoglycosides Coupled with Galactose and Lactose

Polysialoglycoconjugates, such as polysialylated ganglio-series gangliosides and N-CAM (neural cell adhesion molecule), are of interest because of their important physiological functions in association with neural cell development, differentiation, neuron network formation, and so on.^2-4 Chemical synthesis of these glycoconjugates provides an effective method to elucidate their biological significance in nature at the molecular level, providing not only genuine original glycoconjugates but also their derivatives and analogs designed for biological investigation. We have established⁵ an efficient method to construct dimeric and trimeric sialoglycosides by using the lactonated sialic acid derivatives as building blocks, and succeeded in the systematic synthesis of various polysialogangliosides such as GD3, GQ1b, GQlbα and, very recently, GT3.⁶ In this paper, as a part of our continuous synthetic approach directed toward the polysialoglycoconjugates, we report the first synthesis of α-linked tetrameric sialoglycosides coupled with a galactose and lactose residue.     

ACE algorithm for the rapid evaluation of the electron-repulsion integral over Gaussian-type orbitals

A new series of general formulas to evaluate the electron-repulsion integral (ERI) can be derived from modifying the Gauss-Rys quadrature formula. These named as “accompanying coordinate expansion (ACE) formulas” are capable of evaluating very fast ERIs, especially for contracted Gaussian-type orbitals (GTOs). According to the degree of the contraction of GTOs, the optimum formula can be selected among these ACEs. Numerical examples are shown for (ps|ps) and (pp|pp) ERIs as typical examples. It is found that the present ACE algorithm is numerically stable and is most efficient among all algorithms in the literature in the floating-point-operation (FLOP) count for all varieties of the degree of contraction. © 1996 John Wiley & Sons, Inc.     

Molecular Insights into the Antistress Potentials of Brazilian Green Propolis Extract and Its Constituent Artepillin C

Propolis, also known as bee-glue, is a resinous substance produced by honeybees from materials collected from plants they visit. It contains mixtures of wax and bee enzymes and is used by bees as a building material in their hives and by humans for different purposes in traditional healthcare practices. Although the composition of propolis has been shown to depend on its geographic location, climatic zone, and local flora; two largely studied types of propolis: (i) New Zealand and (ii) Brazilian green propolis have been shown to possess Caffeic Acid Phenethyl Ester (CAPE) and Artepillin C (ARC) as the main bioactive constituents, respectively. We have earlier reported that CAPE and ARC possess anticancer activities, mediated by abrogation of mortalin-p53 complex and reactivation of p53 tumor suppressor function. Like CAPE, Artepillin C (ARC) and the supercritical extract of green propolis (GPSE) showed potent anticancer activity. In this study, we recruited low doses of GPSE and ARC (that did not affect either cancer cell proliferation or migration) to investigate their antistress potential using in vitro cell based assays. We report that both GPSE and ARC have the capability to disaggregate metal- and heat-induced aggregated proteins. Metal-induced aggregation of GFP was reduced by fourfold in GPSE- as well as ARC-treated cells. Similarly, whereas heat-induced misfolding of luciferase protein showed 80% loss of activity, the cells treated with either GPSE or ARC showed 60–80% recovery. Furthermore, we demonstrate their pro-hypoxia (marked by the upregulation of HIF-1α) and neuro-differentiation (marked by differentiation morphology and upregulation of expression of GFAP, β-tubulin III, and MAP2). Both GPSE and ARC also offered significant protection against oxidative stress and, hence, may be useful in the treatment of old age-related brain pathologies.     

Crystallization of copper sulphate

Results of the studies of copper sulphate pentahydrate batch crystallization in the temperature range from 70 down to 30 °C are presented. In some of the experiments, free sulphuric acid has been added. The metastable zone width, nucleation and growth kinetic parameters, as well as the system kinetic constant were determined and compared with the data published in the literature.     

Role of the interface in multicomponent materials

Studies of the relationship between interfacial structure and mechanical properties in multicomponent materials are reviewed in this article. The following categories are considered for role of the interface in multicomponent systems: Interpenetrating polymer network(IPN), catalytic effect of silane coupling agent, morphological differences of filler surface, particle-particle interaction and particle size of the filler. The interfacial role in terms of the reinforcement mechanism of the composite and the behavior in the melt state is also discussed in the multicomponent system.     

Classical in-plane negative magnetoresistance and quantum positive magnetoresistance in undoped InSb thin films on GaAs (1 0 0) substrates

Magnetoresistance (MR) effects have been investigated in perpendicular and parallel magnetic fields at 300, 80 K and liquid He temperatures for undoped InSb thin films 0.1–2.3 μm thick grown on GaAs(1 0 0) substrates by MBE. At high temperatures, the intrinsic carriers show the parabolic negative MR observable only in magnetic fields parallel to the film. The skipping-orbit effect due to surface boundary scattering in the classical orbits in the plane vertical to the film has been argued to be responsible for the negative MR. At low temperatures (T=80 K), the transport is dominated by the two-dimensional (2D) electrons in the accumulation layers at the InSb/GaAs(1 0 0) hetero interface; MR is positive and shows a logarithmic increase with anisotropy between parallel and perpendicular field orientation, arising from the 2D weak anti-localization (WAL) that reflects the interplay between the spin-Zeeman effect and strong spin–orbit interaction caused by the asymmetric potential at the interface (Rashba term). The zero-field spin splitting energy of Δ₀13 meV, the electron effective mass of m^*0.10m₀ seven times of the band edge mass in bulk InSb and the effective g-factor of |g^*|15 in the accumulation layer have been inferred from fits of MR for the 0.1 μm thick film to the 2D WL theory.     

Laser spectroscopy of trapped 7Be and 10Be at a prototype slow RI-beam facility of RIKEN

A next-generation slow radioactive nuclear ion beam facility (SLOWRI) which provides slow, high-purity and small emittance ion beams of all elements is being build as one of the principal facilities at the RIKEN RI-beam factory (RIBF). High energy radioactive ion beams from the projectile fragment separator BigRIPS are thermalized in a large gas catcher cell. The thermalized ions in the gas cell are guided and extracted to a vacuum environment by a combination of dc electric fields and inhomogeneous rf fields (rf carpet ion guide). From there the slow ion beam is delivered via a mass separator and a switchyard to various devices: such as an ion trap, a collinear fast beam apparatus, and a multi-reflection time of flight mass spectrometer. In the R&D works at the present RIKEN facility, an overall efficiency of 5% for a 100A MeV ⁸Li ion beam from the present projectile fragment separator RIPS was achieved and the dependence of the efficiency on the ion beam intensity was investigated. Recently our first spectroscopy experiment at the prototype SLOWI was performed on Be isotopes. Energetic ions of ¹⁰Be and ⁷Be from the RIPS were trapped and laser cooled in a linear rf trap and the specific mass shifts of these isotopes were measured for the first time.