Medicinal Flowers. XXXI. Acylated oleanane-type triterpene saponins, Sasanquasaponins I-V, with antiallergic activity from the flower buds of Camellia sasanqua

The methanolic extract and its 1-butanol-soluble fraction from the flower buds of Camellia sasanqua THUNB. were found to show inhibitory activities on the release of β-hexosaminidase from rat basophile leukemia (RBL-2H3) cells. From the 1-butanol-soluble fraction, five new acylated oleanane-type triterpene saponins, sasanquasaponins I-V, were isolated together with a known saponin and their chemical structures were elucidated on the basis of chemical and physicochemical evidence. The principal saponin constituents, sasanquasaponins I-III, with an acyl group at the 22-position of the aglycon part showed the inhibitory effects on the release of β-hexosaminidase and some structure-activity relationships were reported.     

Time variation of the electromagnetic transfer function of the earth estimated by using wavelet transform

In order to accurately estimate the geomagnetic transfer functions in the area of the volcano Mt. Iwate (IWT), we applied the interstation transfer function (ISTF) method to the three-component geomagnetic field data observed at Mt. Iwate station (IWT), using the Kakioka Magnetic Observatory, JMA (KAK) as remote reference station. Instead of the conventional Fourier transform, in which temporary transient noises badly degrade the accuracy of long term properties, continuous wavelet transform has been used. The accuracy of the results was as high as that of robust estimations of transfer functions obtained by the Fourier transform method. This would provide us with possibilities for routinely monitoring the transfer functions, without sophisticated statistical procedures, to detect changes in the underground electrical conductivity structure.     

Cluster carbonyls of the [Re(6)(mu(3)-Se)(8)](2+) core: synthesis, structural characterization, and computational analysis

The reactions of the previously reported cluster complexes [Re(6)(mu(3)-Se)(8)(PEt(3))(5)I]I, trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)], and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)] with the [Re(6)(mu(3)-Se)(8)](2+) core with CO in the presence of AgSbF(6) afforded the corresponding cluster carbonyls [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CO)][SbF(6)](2) (), trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (), and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between and indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.     

Synthesis of oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)] and anomalous proton conductivities of the thin films

New proton-conductive polyamide oligomers, oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)], were synthesized to investigate the proton transport properties of bulk and thin films. The obtained oligomers were characterized by the X-ray diffraction, FT-IR spectra, ¹H NMR, Matrix Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrum, and electrical conductivity measurements. The bulk proton conductivity is 3.0 × 10^? 4 S cm^? 1 at the relative humidity (RH) of 80%. The proton conductivity of thin film is relatively higher than that of bulk sample. Thickness dependence of the proton conductivity was observed in these thin films. The maximum proton conductivity of the thin film is 4.0 × 10^? 3 S cm^? 1 at the relative humidity (RH) of 80%, which is higher one order magnitude than that of the bulk sample. The activation energies of bulk and 200 nm thick film are 1.0 and 0.69 eV at the RH of 60%, respectively.     

Enantioselective Darzens reaction using organoselenide-lithium hydroxide complexes

Asymmetric Darzens reaction catalyzed by chiral selenides is described. A novel Lewis acid/Brønsted base catalyst formed by C₂ symmetric chiral selenide-bearing isoborneol skeletons, which were readily prepared from (1S)-10-camphorsulfonic acid, and LiOH promoted the reaction of phenacyl bromide with aldehydes to afford the desired trans oxiranes with up to 62% ee.     

Oxygen‐sensing properties of 5,10,15,20‐tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate)

A novel methacrylate monomer bearing 5,10,15,20‐tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a ) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2‐trifluoroethyl methacrylate (TFEM) to give poly (IBM‐co‐TFEM) bearing PdTPP (copolymer 2a ) as a dye‐conjugated oxygen‐permeable polymer for pressure‐sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV–vis spectroscopy and extended X‐ray absorption fine structure analysis. The Stern–Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM‐co‐TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b ) previously reported. The plots were successfully fitted with a two‐site model to give two distinct Stern–Volmer constants (K_SV1 and K_SV2) and the partition ratio f₁. Interestingly, the f₁ values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM‐co‐TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature‐dependent and the other temperature‐independent, in the mixture of PdTPP and poly(IBM‐co‐TFEM). The dye‐conjugation approach effectively eliminates the temperature‐dependent, but not the temperature‐independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature‐dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature‐independent one appears to be inherent nature in PdTPP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 663–670, 2010     

Formation of a liquid organic ion associate in aqueous solution and its application to the GF-AAS determination of trace cadmium in environmental water as a complex with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol

The formation of a liquid organic ion associate in an aqueous sample was applied to the concentration and determination of cadmium in environmental water samples. Cadmium was converted into a complex with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol (5-Br-PAPS) in a 40-mL sample solution, and was extracted into a liquid ion associate of phenolsulfonate and benzethonium during phase formation. More than 400-fold enrichment was easily attained by this technique, because the volume of the liquid organic phase formed was very small, ca. 2 microL. After dilution of the organic phase with a small volume of 2-methoxyethanol, the cadmium in the solution was determined by GF-AAS. The detection limit was 0.09 ng/L (3sigma(b)). This method was applied to the determination of cadmium in river water and seawater.     

Antiplane shear problems of perfect and partially damaged matrix-inclusion systems

Summary Antiplane shear problem of an infinite medium containing a circular inclusion of different material is investigated in this article. Perfectly bonding between the matrix and the inclusion, as well as partial debonding in the form of a circumferential crack occurring at the interface of these two constituents, are considered. Using the complex variable method in conjunction with a semi-inversed technique, exact expressions for the stress, displacement and stress intensity factor in the problem are obtained for various external loading conditions, including that brought about by stress singularities. A number of numerical results of stress intensity factors for a partially damaged matrix-inclusion system are given, and a discussion is made on the general features of the antiplane shear problem of inhomogeneous matrix-inclusion systems.

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Scherung von perfekten und teilweise beschädigten Matrix-Einschluß-Systemen außerhalb der Ebene

Übersicht In dieser Abhandlung wird das Problem der Scherung au\erhalb der Ebene für einen unendlichen Körper mit einem kreisförmigen Einschluß aus unterschiedlichem Material untersucht. Es wird die perfekte Verbindung zwischen der Matrix und dem Einschluß ebenso wie teilweise Ablösung in der Form eines Umkreisrisses an der Schnittfläche zwischen den beiden Bestandteilen betrachtet. Unter Verwendung der komplexen Variablenmethode in Verbindung mit einem Halbinversionsverfahren werden exakte Ausdrücke für Spannung, Verschiebung und Spannungsintensitätsfaktor für verschiedene äußere Belastungszustände, einschließlich dem Einfluß von Spannungssingularitäten, erhalten. Es werden numerische Ergebnisse für den Spannungsintensitätsfaktor für ein teilweise beschädigtes Matrix-Einschluß-System gegeben, und die allgemeine Form des Problems der Scherung außerhalb der Ebene für ein nicht homogenes Matrix-Einschluß-System wird diskutiert.

     

Evaluation of the abilities of ��-cyclodextrin to form complexes by surface plasmon resonance with a Biacore? system

Although phase-solubility studies have often been used to evaluate the interaction of cyclodextrins (CDs) with various drugs, hundreds of milligrams of both CD and drug are required to prepare a phase diagram. A method that would require considerably less material for evaluating complex formation between a CD and guest compound is therefore needed. We previously reported the detection of the interactions between ??-CD and various drugs using a Biacore^® system. In this study, we succeeded in immobilizing 6-monodeoxy-6-monoamino-??-CD on the gold surface of a sensor chip and in detecting the interactions between the immobilized ??-CD and various drugs. The interaction processes were kinetically analyzed using Biacore^®. The surface plasmon resonance sensorgrams indicated that the association and dissociation rates of the interactions between ??-CD and drugs were faster than those between ??-CD and drugs. Although the association constants calculated from the sensorgrams were smaller than those calculated from phase-solubility studies, good correlation was shown between these data.