Triterpenoid Constituents of Huperzia miyoshiana

Thirteen triterpenoids, including three new ones, miyoshianois A (1), B (2) and C (3), were isolated from Huperzia miyoshiana. The structures of these new compounds were established as 3-O-dihydroferuloyltohogenol (1), 16-oxo-3β,21β-dihydrox-y-serrat-14-en-24-ferulate (2) and 16-oxo-3a, 21β-dihydroxy-serrat-14-en-24-ferulate (3), respectively, on the basis of their spectroscopic analysis.     

Numerosities of labelled sets: a new way of counting

The notions of “labelled set” and “numerosity” are introduced to generalize the counting process of finite sets. The resulting numbers, called numerosities, are then used to develop nonstandard analysis. The existence of a numerosity function is equivalent to the existence of a selective ultrafilter, hence it is independent of the axioms of ZFC.     

Gradient‐enhanced one‐dimensional pulse schemes for quaternary and methylene carbon detection

Gradient‐enhanced pulse schemes are presented for the detection of quaternary and methylene carbons. The new pulse schemes permit the detection of quaternary and methylene (—CH₂) carbons or CH₂ carbons alone from a single experiment. Efficient suppression of CH and CH₃ carbons in all the pulse schemes is achieved by creating their antiphase magnetization and then dephasing using gradients. In the pulse schemes for detection of only CH₂ carbons, the quaternary carbons are also suppressed either by dephasing using gradients or by rendering them unobservable by retaining in longitudinal order. The experimental results of the gradient pulse schemes are demonstrated on cholesteryl acetate and cyclosporin A. These one‐dimensional techniques, because of their simplicity and the ease of performing the experiments, can be important for routine chemical applications. Copyright © 2003 John Wiley & Sons, Ltd.     

Measurability implies continuity for solutions of functional equations - even with few variables

Summary. We prove that - under certain conditions - measurable solutions $f$ of the functional equation $f(x)=h(x,y,f(g_{1}(x,y)),\ldots,f(g_{n}(x,y))),\quad(x,y)\in D \subset \mathbb{R}^{s} \times \mathbb{R}^{l}$ are continuous, even if $1\le l\le s$. As a tool we introduce new classes of functions which - roughly speaking - interpolate between continuous and Lebesgue measurable functions. Connection between these classes are also investigated.     

Limits of tangents and minimality of complex links

We show that the complex link of a large class of space germs (X,x₀) is characterized by its “simplicity”, among the Milnor fibres of functions with isolated singularity on X. This amounts to the minimality of the Milnor number, whenever this number is defined. Such a phenomenon has been first pointed out in case (X,x₀) is an isolated hypersurface singularity, by Teissier (Cycles évanescents, sections planes et conditions de Whitney, in: Singularités à Cargèse 1972, Asterisque, Nos. 7 et 8, Soc. Math. France, Paris, 1973, pp. 285-362).     

Pressure-induced polymorphism in enstatite (MgSiO3) at room temperature: clinoenstatite and orthoenstatite

The phase transition of a synthetic clinoenstatite in a diamond-anvil cell has been studied by using Raman spectroscopy at various pressures and room temperature. The phenomena observed in clinoenstatite have been compared with that observed in orthoenstatite. It is found that the pressure-induced phase transitions in the two enstatites are reversible, but with different transition pressures and transition behavior. An analysis of Raman spectra has revealed that the two enstatites have different high-pressure polymorphs. This result suggests that the space group of the high-pressure polymorph of orthoenstatite is not of C2/c, and that orthoenstatite and orthoferrosilite have different transition routes at room temperature and high pressure. The compressional behavior of the high-PC2/c enstatite is also discussed according to the pressure dependences of Raman frequencies.     

Assignment of chemical shifts in benzohydroxamic acid and structure of its silylated derivatives by 15N enrichment

¹⁵N isotopic enrichment was necessary for the unequivocal assignment of the ¹H NMR lines to the protons in the NH–OH fragment of benzohydroxamic acid, BHXA, C₆H₅CONHOH, in dry dimethyl sulfoxide solutions. The assignment [δ(NH) = 11.21, δ(OH) = 9.01, ¹J(¹⁵N,¹H) = 102.2 Hz, ²J(¹⁵N,¹H) <1.5 Hz], which is opposite to that used by other authors, confirms the assignment extended to BHXA by Brown and co‐workers from the spectra of acetohydroxamic acid. The enrichment allowed also assignment of the ²⁹Si lines in the spectra of disilylated benzohydroxamic acid, (Z)‐tert‐butyldimethylsilyl N‐tert‐butyldimethylsilyloxybenzoimidate (2) and (Z)‐tert‐butyldiphenylsilyl N‐tert‐butyldiphenylsilyloxybenzoimidate (3), and confirmed structure of the monosilylated products, N‐tert‐butyldiphenylsilyloxybenzamide (4) and N‐tert‐butyldiphenylsilyloxy benzoimidic acid (5). Copyright © 2003 John Wiley & Sons, Ltd.     

Topological analysis of charge density in heptasulfur imide (S7NH) from isolated molecule to solid

Intra and intermolecular interactions of heptasulfur imide (S₇NH) are investigated in terms of topological properties analyses, such analyses are applied to both experimental (multipole model) and theoretically calculated (DFT and PDFT calculations) charge densities of the isolated molecule and of the crystal. The same analyses are also applied to a multipole model density obtained from theoretically (PDFT) derived structural amplitudes. The covalent bond character of S-N, N-H and S-S bonds are well described in terms of density, ρ_b, and total energy density, H_b, at the bond critical point r_c, though it is clear that the S-S bonds are weaker shared interactions than those of N-H and S-N bonds. Lone pair electron regions of sulfur and nitrogen atoms are revealed as the local charge concentration site from the Laplacian of charge density. The even weaker intermolecular interactions are well characterized; these include the N-H?S hydrogen bonding, N?S binding interactions and S?S binding interactions. All these intermolecular binding interactions are closed-shell interactions. The Laplacian of charge density demonstrates a directional intermolecular binding interaction. The corresponding intermolecular binding energies are derived by MP2/6-311+G(d,p) calculations. Atomic graph of each atom of the molecule is described in detail by the vertices, edges and faces of the polyhedron around the nucleus to illustrate such directional interactions.     

Investigation of the effect of CdCl2 processing on vacuum deposited CdS/CdTe thin film solar cells by DLTS

Thin film CdS/CdTe solar cells have been prepared by conventional vacuum deposition technique. Deep level transient spectroscopy (DLTS), temperature and frequency dependent capacitance-voltage (C-V) measurements were utilised to investigate the performance limiting defect states in the CdTe layer subjected to the post deposition treatments such as CdCl₂-dipping and/or annealing in air. Five hole traps, all of which have been previously reported in the literature, were identified in as-grown CdTe at 0.19, 0.20, 0.22, 0.30 and 0.40 eV above the valence band. A single hole trap level has been evidenced at 0.45 eV after both post deposition heat and CdCl₂ treatments.     

NMR studies on a palladium(II) complex containing an incompletely coordinated facultative pentadentate Schiff base ligand

Palladium(II) dichloride reacts with 1,10‐bis(2‐pyrrolyl)‐2,5,9‐triaza‐1,9‐decadiene to give a [Pd(C₁₅H₂₀N₅)]Cl complex in which the ligand is four‐coordinated, leaving one pyrrole group dangling. By using COSY, gHSQC, gHMBC connectivities and NOE experiments it has been concluded that one linkage isomer exists in DMSO solution, in spite of the fact that different sets of N atoms of potentially pentadentate ligand might be involved in coordination, and that the three chelate rings in the complex cation are arranged in a sequence: five‐membered, six‐membered, five‐membered which is different from that (5–5–6) found by x‐ray studies on the related [Ni(C₁₅H₂₀N₅)]Cl compound. NMR studies allowed an unambiguous assignment of all ¹H and ¹³C NMR resonances for the complex. Results of x‐ray structural analysis of [Pd(C₁₅H₂₀N₅)](CH₃COO)H₂O supported the five‐membered, six‐membered, five‐membered ring sequence in the [Pd(C₁₅H₂₀N₅)]⁺ complex cation and show an E (trans) orientation of the dangling pyrrole group with respect to the metal center. Copyright © 2002 John Wiley & Sons, Ltd.