Structures of novel norstilbene dimer, longusone A, and three new stilbene dimers, longusols A, B, and C, with antiallergic and radical scavenging activities from Egyptian natural medicine Cyperus longus

The methanolic extract of the whole plant of Cyperus longus originating in Egypt was found to show antiallergic effect on ear passive cutaneous anaphylaxis reactions in mice. By bioassay-guided separation, 11 stilbenes and stilbene dimers including a novel norstilbene dimer, longusone A, and three new stilbene dimers, longusols A, B, and C, were isolated. Their structures were elucidated on the basis of chemical and physicochemical evidence. Among the isolates, longusol B (IC(50)=96 μM), luteolin (3.0 μM), resveratrol (17 μM), piceatannol (24 μM), and cassigarols E (84 μM) and G (84 μM) were found to inhibit the release of β-hexosaminidase, as a marker of antigen-induced degranulations, in rat basophilic leukemia (RBL-2H3) cells. In addition, the methanolic extract and the constituents showed 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity (SC(50)=22 μg/ml and 2.8-29 μM, respectively).     

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.     

Investigation of void formation beneath thin AlN layers by decomposition of sapphire substrates for self-separation of thick AlN layers grown by HVPE

Void formation at the interface between thick AlN layers and (0 0 0 1) sapphire substrates was investigated to form a predefined separation point of the thick AlN layers for the preparation of freestanding AlN substrates by hydride vapor phase epitaxy (HVPE). By heating 50–200 nm thick intermediate AlN layers above 1400 °C in a gas flow containing H₂ and NH₃, voids were formed beneath the AlN layers by the decomposition reaction of sapphire with hydrogen diffusing to the interface. The volume of the sapphire decomposed at the interface increased as the temperature and time of the heat treatment was increased and as the thickness of the AlN layer decreased. Thick AlN layers subsequently grown at 1450 °C after the formation of voids beneath the intermediate AlN layer with a thickness of 100 nm or above self-separated from the sapphire substrates during post-growth cooling with the aid of voids. The 79 μm thick freestanding AlN substrate obtained using a 200 nm thick intermediate AlN layer had a flat surface with no pits, high optical transparency at wavelengths above 208.1 nm, and a dislocation density of 1.5×10⁸ cm⁻².     

On the Fourier coefficients of Hilbert-Maass wave forms of half integral weight over arbitrary algebraic number fields

The purpose of this paper is to derive a generalization of Shimura's results concerning Fourier coefficients of Hilbert modular forms of half integral weight over total real number fields in the case of Hilbert-Maass wave forms over algebraic number fields by following the Shimura's method. Employing theta functions, we shall construct the Shimura correspondence Ψ_τ from Hilbert-Maass wave forms f of half integral weight over algebraic number fields to Hilbert-Maass wave forms of integral weight over algebraic number fields. We shall determine explicitly the Fourier coefficients of in terms of these f. Moreover, under some assumptions about f concerning the multiplicity one theorem with respect to Hecke operators, we shall establish an explicit connection between the square of Fourier coefficients of f and the central value of quadratic twisted L-series associated with the image of f.     

Selective Michael Reaction Controlled by Supersilyl Protecting Group

Selective Michael reaction of organolithium reagents to supersilyl methacrylate is reported. The method was able to control a single and double Michael addition. The successful termination of the process using the supersilyl protecting group allows for the controlled, chemoselective, and diastereoselective Michael reaction.     

Langmuir-Blodgett films of a Mo-blue nanoring [Mo(142)O(429)H(10)(H(2)O)(49)(CH(3)CO(2))(5)(CH(3)CH(2)CO(2))](30)(-) (Mo(142)) by the semiamphiphilic method

Langmuir monolayers and LB films of the ring-shaped mixed-valence polyoxomolybdate [Mo142O429H10(H2O)49(CH3CO2)5(CH3CH2CO2)](30-) (Mo142) dissolved in the aqueous subphase have been successfully fabricated by using the adsorption properties of a DODA monolayer. Infrared and ultraviolet-visible spectroscopy of the LB films indicates that Mo142 and DODA molecules are incorporated within these LB films. X-ray reflectivity experiments indicate that the LB films exhibit a well-defined lamellar structure formed by bilayers of DODA molecules alternating with monolayers of Mo142. Using behenic acid-modified hydrophobic quartz substrate is critical for the formation of the well-defined lamellar structure. From the values of the periodicity obtained by these experiments it is clear that the Mo142 clusters lie flat along the charged organic layers. AFM images also showed the flat and homogeneous films on the quartz substrates treated with behenic acid. Cyclic voltammograms of Mo142-LB films deposited on ITO substrates showed quasi-reversible oxidation/reduction waves with positive shift of the potential compared to the case of solution.     

Structure Revision of Caesalpinistas A and B and Isolation of a New Furanoditerpenoid from the Cotyledons of Caesalpinia decapetala var. japonica

A known cassane‐type furanoditerpenoid, caesalpinista B ( 1 ), and a new diterpenoid, deoxycaesaljaponin A ( 2 ), were isolated from the cotyledons of Caesalpinia decapetala var. japonica. The previously reported configurational assignments of 1 and the related diterpenoid caesalpinista A ( 3 ) were revised on the basis of X‐ray crystallography and chemical conversion. The structure of 2 was elucidated by spectroscopic data and chemical conversion into 3 .     

Intramolecular and liquid structure of 2,2,2-trifluoroethanol by X-ray diffraction

Intramolecular and liquid structure of 2,2,2-trifluoroethanol (TFE) have been investigated by x-ray diffraction at 25°C. The structural parameters for the skeleton of the molecules in the liquid phase are similar to those in the gas phase. The conformers of TFE molecules in the liquid phase are discussed. The O...O distance at about 284 pm and additional F...O one at about 302 pm were found to be characteristic for the first neighbor interactions. Various models (dimers and trimers) have been examined for analyzing the first neighbor structure. The liquid structure was explained in terms of small clusters consisting of two to three molecules rather than of a more extended polymeric network.Central Research Institute for Chemistry of the Hungarian Academy of Sciences, Budapest, P. O. Box 17, H-1525, Hungary.     

Tris(trimethylsilyl)silyl-governed aldehyde cross-aldol cascade reaction

The use of the tris(trimethylsilyl)silyl (TTMSS) group in aldehyde-derived silyl enol ethers affords aldehyde cross-aldol products with high yields and allows for unprecedented reactivity. The reaction is catalyzed by 0.05 mol % of HNTf2, and can easily be managed to give beta,delta-bis-, beta,delta,gamma-tris-, and beta,delta,zeta-tris-hydroxy-aldehydes with extremely high selectivity by simple stoichiometric control. High diastereoselectivity is obtained in all cases, and the use of chiral aldehydes affords Felkin products when there are nonchelating substituents, chelation products when there is a chelating sbustituent, and syn products when there is beta-substitution. HNTf2 is proposed to be an initiator, and highly Lewis acidic TTMSSNTf2 is the true catalyst.