Ecdysteroid acetates fromAjuga reptans

The compounds 20-hydroxyecdysone-22-acetate and viticosterone E (20-hydroxyecdysone-25-acetate) are observed for the first time inAjuga reptans L. growing at the northern limit of its range in a middle taiga subzone of European northeastern Russia. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–610, September–October, 1999.     

Diagram rigidity for geometric amalgamations of free groups

In this paper, we show that a class of 2-dimensional locally CAT(-1) spaces is topologically rigid: isomorphism of the fundamental groups is equivalent to the spaces being homeomorphic. An immediate application of this result is a diagram rigidity theorem for certain amalgamations of free groups. The direct limits of two such amalgamations are isomorphic if and only if there is an isomorphism between the respective diagrams.     

Detection of 20‐hydroxyecdysone in calf urine by comparative liquid chromatography/high‐resolution mass spectrometry and liquid chromatography/tandem mass spectrometry measurements: application to the control of the potential misuse of ecdysteroids in cattle

Ecdysteroids, which are steroid hormones in invertebrates, but which are also present in plants, could potentially be used as anabolic agents in food‐producing animals. The control of ecdysteroid misuse in cattle relies on the development of an efficient method for their detection in biological matrices at trace levels (µg L⁻¹). In order to propose an analytical procedure dedicated to the identification of excreted 20‐hydroxyecdysone (20E) in urine and faecal samples of breeding animals, a comparative study of the spectrometric behaviour of these compounds was carried out both by LC/(ESI‐)/HRMSⁿ (hybrid linear ion trap – orbital trap) and by LC/(ESI+)/MS/MS (triple quadrupole). This study revealed the formation of a large number of product ions both in positive and negative ion mode, corresponding to losses of water molecules and specific cleavages on the side chain. The sample preparation consisted of sequential purification on two solid‐phase extraction cartridges (SPE octadecylsilyl and SPE silica). The detection limits were around 0.5 µg L⁻¹ in the selected reaction monitoring (SRM) mode and recoveries above 60% were obtained. The method was successfully applied to the analysis of real samples collected from calves treated with 60 mg 20E over 4 days. Analysis of the samples allowed the investigation of the kinetics of elimination of 20E in calf urine and determination of the time‐frame for the control of potential abuse. Copyright © 2008 John Wiley & Sons, Ltd.     

Obtention d'hétérocycles par action de binucléophiles diazotés sur des chalcones: Influence du substituant en position 2

Reactivity of 2-susbituted chalcones against diaza binucleophiles (hydrazines, thiourea, guanidine) has been studied. Various heterocycles (pyrazoles, pyrazolines, pyrimidines) or substituted hydrazines were obtained. A general interpretation is given according to the substituent of the enone system, R, the nature of binucleophile and the medium.     

Synthesis of mixed metallic nanoparticles by spark discharge

Short spark discharges (2 μs) were successfully applied to generate mixed particles a few nanometres in diameter by fast quenching. Alloyed Cr–Co electrodes were applied to demonstrate this. Further it was shown that if the anode and the cathode are different materials, the discharge process mixes the vapour of both materials, forming mixed nanoparticles. Electron microscopy (TEM, SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analyses were performed on the collected particles to study their size, morphology, composition and structure. The average compositions of the particles were measured by inductively coupled plasma (ICP). In addition, online measurements of the particle size distribution by mobility analysis were carried out. In the case of alloyed electrodes (Cr–Co), the relative concentration of the elements in the nanoparticulate sample was consistent with the electrode composition. When using electrodes of different metals (Au–Pd and Ag–Pd) the individual nanoparticles showed a range of mixing ratios. No surface segregation was observed in these mixed noble metal particles. Crystalline nanoparticulate mixed phases were found in all cases.     

Generation of nanoparticles by spark discharge

The production of nanoparticles by microsecond spark discharge evaporation in inert gas is studied systematically applying transmission electron microscopy, mobility analysis and BET surface area measurement. The method of spark discharge is of special interest, because it is continuous, clean, extremely flexible with respect to material, and scale-up is possible. The particle size distributions are narrow and the mean primary particle size can be controlled via the energy per spark. Separated, unagglomerated particles, 3–12 nm in size, or agglomerates can be obtained depending on the flow rate. The nanoparticulate mass produced is typically 5 g/kWh. A formula is given, which estimates the mass production rate via thermal conductivity, evaporation enthalpy and the boiling point of the material used. We showed that with gas purified at the spot, the method produced gold particles that were so clean that sintering of agglomerated particles occurred at room temperature. The influence of a number of parameters on the primary particle size and mass production rate was studied and qualitatively understood with a model of Lehtinen and Zachariah (J Aerosol Sci 33:357–368, 2002). Surprisingly high charging probabilities for one polarity were obtained. Spark generation is therefore of special interest for producing monodisperse aerosols or particles of uniform size via electrical mobility analysis. Qualitative observations in the present study include the phenomenon of material exchange between the electrodes by the spark, which opens the possibility of producing arbitrary mixtures of materials on a nanoscale. If spark generation of nanoparticles is performed in a standing or almost standing gas, an aerogel of a web-like structure forms between surfaces of different electrical potential.     

Rigidity Result for Certain Three-Dimensional Singular Spaces and Their Fundamental Groups

In this paper, we introduce a particularly nice family of locally CAT(−1) spaces, which we call hyperbolic P-manifolds. For X³ a simple, thick hyperbolic P-manifold of dimension 3, we show that certain subsets of the boundary at infinity of the universal cover of X³ are characterized topologically. Straightforward consequences include a version of Mostow rigidity, as well as quasi-isometry rigidity for these spaces.     

Asymmetric hydrogenation of α-amino acid precursors with a new chiral diphosphine (dioxop) derived from 1,6-D-anhydroglucose

High optical yields are obtained in the hydrogenation of α-amino acid precursors rising [Rh(COD)dioxop] + ClO₄^? in presence of triethylamine as catalyst.