Chemical composition of the pods of Albizia polyphylla

In this study, we report for the first time the presence of alkaloids belonging to β-carboline type in the pods of the endemic Albizia polyphylla from Madagascar. Three major alkaloids were isolated and structurally identified as: 1-methyl-β-carboline, (+)-(R)-1-methyl-1,2,3,4-tetrahydro-β-carboline and (–)-(S)-1,2-dimethyl-1,2,3,4-tetrahydro-β-carboline.     

Operators that attain their minima

In this paper we study the theory of operators on complex Hilbert spaces, which attain theirminima in the unit sphere. We prove someimportant results concerning the characterization of the N*, and also AN* operators, see respectively Definition 1.1 and Definition 1.4. The injective property plays an important role in these operators, and shall be established by these classes.     

Poly(oxanorbornenedicarboximide)s dendronized with amphiphilic poly(alkyl ether) dendrons

Attaching dendritically branched side chains to each repeat unit of a linear polymer produces molecular building blocks of nanometer‐sized dimensions called dendronized polymers. The structure of these complex molecular architectures is highly tunable and, therefore, of interest for a wide range of potential applications. The first examples of dendronized polymers prepared by living ring‐opening metathesis polymerization of oxanorbornenedicarboximide macromonomers with poly(alkyl ether) dendrons are reported. Small‐angle X‐ray scattering experiments on bulk samples confirm that the diameter of the individual cylindrical polymers can be tailored by the choice of dendron generation or the length of the hydrocarbon peripheral group. Analysis of the SAXS data based on a core‐shell model indicates that although the diameter of the cylinder increases with generation, the size of the core does not change; this suggests that these dendrons only loosely encapsulate the polymer backbone. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3221–3239     

Fe- and Cu-oxides supported on γ-Al2O3 as catalysts for the selective catalytic reduction of NO with ethanol. Part I: catalyst preparation,characterization, and activity

Fe- and Cu-oxides supported on γ-alumina (γ-Al₂O₃; metal loading of 3 mass %) were investigated as alternative catalysts to the conventional Ag-based system in the selective catalytic reduction of NO with ethanol (EtOH-SCR). The catalysts were characterized by elemental analysis, N₂ sorption, X-ray diffraction, temperature-prgrammed desorption of NH₃, temperature-programmed reduction with H2, diffuse reflectance UV-VIS (DR-UV-VIS) spectroscopy, and compared with 3 mass % Ag/γ-Al₂O₃ as a reference catalyst. Catalytic experiments were carried out between 423 K and 773 K in the steady state and by temperature-programmed surface reaction (TPSR) experiments. For all catalysts, the highest NO conversion (900 ppm (ppm = parts of the mixture component per million parts of all mixture components) NO, 900 ppm EtOH, 0.5 vol. % H₂O, 4 vol. % O₂ in He) was found at 573 K. While 84 % of NO were converted over the Ag-based catalysts, only 20–60 % NO conversion was observed for the Fe- and Cu-containing catalysts. Total oxidation of ethanol as an unwanted side reaction occurs over 3 mass % Cu on γ-Al₂O₃ already at 573 K, whereas the highest activity of 3 mass % Fe on γ-Al₂O₃ for this conversion was reached at 743 K. For lower temperatures, partial oxidation of ethanol leads to organic by-products which can act as active intermediates in EtOH-SCR. TPSR experiments show that ethanol reacts over both the Fe- and the Cu-based catalysts to organic by-products, such as ethene or acetaldehyde, which affect the EtOH-SCR reaction.     

Application of splines for determining the velocity characteristic of a medium from a vertical seismic survey

A method for solving the inverse kinematic problem of determining the velocity characteristic of a medium from a vertical seismic survey, is proposed. It is based on the combined use of the eikonal equation and spline methods of approximation for multivariable functions. The problem is solved by assuming a horizontally stratified medium; no assumptions about the number of layers and their thickness are made. First, using the data of the first arrival times of the seismic signal from several shotpoints, which are registered by detectors located in the vertical borehole, a spline approximating the function of first arrival time of the signal from source points to any point in the Earth subsurface is constructed. Then with the help of the eikonal equation, the characteristic of the medium around the borehole is determined. Numerical experiments on the model and the real data show high efficiency of the proposed method.     

Surface nanostructuring of metals by laser irradiation: effects of pulse duration, wavelength and gas atmosphere

Surface modifications by nanostructuring present a new laser application for improvement of surface properties such as adhesion, mechanical characteristics or corrosion protection. In this study, we report the formation of nanoparticles by laser irradiation of a steel surface. The influence of laser parameters such as pulse duration (25–30 ns, 500 fs), wavelength (248 nm, 308 nm), and the background gas pressure (10 mbar-1 bar) on the formation of this back deposition layer composed of aggregated iron oxide nanoparticles were investigated. Scanning electron microscopy and atomic force microscopy were used to characterise the irradiated steel surface and the particle morphology deposited by backward flux. In the nanosecond laser ablation regime, films are formed by aggregated nanoparticles with well developed cauliflower like structures, the size and the morphology depending on the nature and pressure of the background gas. In the femtosecond regime, we observed the formation of micrometer sized structures at the steel surface. In particular, a non-conventional mechanism of nanocluster condensation and growth is revealed since two different ablation rates corresponding to two different predominant processes are observed. These analyses demonstrate the possibility of controlling the distribution and the size of particles by varying the laser parameters and the background gas pressure and nature. PACS 52.38.Mf; 81.65.-b; 81.15.Gh.     

Synthesis of Branched‐Chain Sugars with a DHAP‐Dependent Aldolase: Ketones are Electrophile Substrates of Rhamnulose‐1‐phosphate Aldolases

Dihydroxyacetone phosphate (DHAP)‐dependent rhamnulose aldolases display an unprecedented versatility for ketones as electrophile substrates. We selected and characterized a rhamnulose aldolase from Bacteroides thetaiotaomicron (RhuABthet) to provide a proof of concept. DHAP was added as a nucleophile to several α‐hydroxylated ketones used as electrophiles. This aldol addition was stereoselective and produced branched‐chain monosaccharide adducts with a tertiary alcohol moiety. Several aldols were readily obtained in good to excellent yields (from 76 to 95 %). These results contradict the general view that aldehydes are the only electrophile substrates for DHAP‐dependent aldolases and provide a new C?C bond‐forming enzyme for stereoselective synthesis of tertiary alcohols.     

Peptide analysis of tooth enamel – A sex estimation tool for archaeological,anthropological, or forensic research

Proteomics has become an attractive method to study human and animal material, biological profile, and origin as an alternative to DNA analysis. It is limited by DNA amplification in ancient samples and its contamination, high cost, and limited preservation of nuclear DNA. Currently, three approaches are available to estimate sex–osteology, genomics, or proteomics, but little is known about the relative reliability of these methods in applied settings. Proteomics provides a new, seemingly simple, and relatively non-expensive way of sex estimation without the risk of contamination. Proteins can be preserved in hard teeth tissue (enamel) for tens of thousands of years. It uses two sexually distinct forms of the protein amelogenin in tooth enamel detectable by liquid chromatography-mass spectrometry; the protein amelogenin Y isoform is present in enamel dental tissue only in males, while amelogenin isoform X can be found in both sexes. From the point of view of archaeological, anthropological, and forensic research and applications, the reduced destruction of the methods used is essential, as well as the minimum requirements for sample size.     

Lead(II) Formate in Rembrandt's Night Watch: Detection and Distribution from the Macro- to the Micro-scale

The Night Watch, painted in 1642 and on view in the Rijksmuseum in Amsterdam, is considered Rembrandt's most famous work. X-ray powder diffraction (XRPD) mapping at multiple length scales revealed the unusual presence of lead(II) formate, Pb(HCOO)₂, in several areas of the painting. Until now, this compound was never reported in historical oil paints. In order to get insights into this phenomenon, one possible chemical pathway was explored thanks to the preparation and micro-analysis of model oil paint media prepared by heating linseed oil and lead(II) oxide (PbO) drier as described in 17^th century recipes. Synchrotron radiation based micro-XRPD (SR-μ-XRPD) and infrared microscopy were combined to identify and map at the micro-scale various neo-formed lead-based compounds in these model samples. Both lead(II) formate and lead(II) formate hydroxide Pb(HCOO)(OH) were detected and mapped, providing new clues regarding the reactivity of lead driers in oil matrices in historical paintings.